Organic electroluminescent materials and devices

Abstract

The present invention relates to organic electroluminescent materials and devices. Provided are organometallic compounds comprising a central metal atom complexed with at least a bidentate ligand comprising at least two 5- to 10-membered carbocyclic or heterocyclic rings connected by a direct bond. Also provided are compositions comprising these organometallic compounds. Further provided are organic light emitting devices (OLEDs) and related consumer products utilizing these organometallic compounds.

Description

[0001] Cross-reference of related applications

[0002] This application claims priority to U.S. Provisional Application No. 63 / 756,839, filed February 11, 2025, pursuant to 35 USC §119(e), the entire contents of which are incorporated herein by reference. Technical Field

[0003] This disclosure generally relates to organic or metal coordination compounds and compositions and their various uses, including as emitters, sensitizers, charge transporters or exciton transporters in devices such as organic light-emitting diodes and related electronic devices and consumer products. Background Technology

[0004] For various reasons, optoelectronic devices utilizing organic materials are becoming increasingly popular. Many of the materials used to manufacture these devices are relatively inexpensive, thus organic optoelectronic devices have the potential to offer a cost advantage over inorganic devices. Furthermore, the inherent properties of organic materials, such as their flexibility, make them more suitable for specific applications, such as fabrication on flexible substrates. Examples of organic optoelectronic devices include organic light-emitting diodes / devices (OLEDs), organic phototransistors, organic photovoltaic cells, organic scintillators, and organic photodetectors. For OLEDs, organic materials can offer performance advantages over conventional materials.

[0005] OLEDs utilize organic thin films that emit light when a voltage is applied to the device. OLEDs are becoming an increasingly popular technology for applications such as displays, lighting, and backlighting.

[0006] One application of emitting molecules is in full-color displays. Industry standards for such displays require pixels suited to emitting specific colors (called "saturated" colors). Specifically, these standards require pixels saturated with red, green, and blue light. Alternatively, OLEDs can be designed to emit white light. In conventional liquid crystal displays, absorption filters are used to filter the emission from a white backlight to produce red, green, and blue emission. The same technology can be used for OLEDs. White OLEDs can be single-emitting-layer (EML) devices or stacked structures. Color can be measured using the CIE coordinate system, well-known in the field. Summary of the Invention

[0007] In one aspect, this disclosure provides a compound having a first ligand L comprising the structure of formula I. A :

[0008] , Formula I;

[0009] Structural parts A and B are each independently a single-ring ring or a multi-ring fused ring system, wherein each ring in the single-ring ring or multi-ring fused ring system is independently a 5- to 10-membered carbon ring or heterocyclic ring.

[0010] Where K 1 and K 2 Each is independently selected from direct bonds, O, S, N(R) α ), P(R α ), B(R) α ), C(R α (R) β ) and Si(R α (R) β );

[0011] Z 1 Selected from BR C C=O, C=S, C=Se, GaR C SiR C R C′ and GeR C R C′ ;

[0012] Z 2 Selected from NR D O and S;

[0013] Where X 1 To X 5 Each can be independently represented as C or N;

[0014] Where R A and R B Each can be independently represented from single substitution to the maximum permissible substitution or no substitution;

[0015] Where R α R β R A R B R C R C’ and R D Independently hydrogen or a substituent selected from the following: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silalkyl, germanalkyl, boronalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphinyl, boronyl, selenyl, and combinations thereof;

[0016] Where R α R β R A R B R C R C’and R D Any two of them can join or fuse to form a ring;

[0017] in Is it a single bond or a double bond?

[0018] Where L A Fit to metal M;

[0019] Metal M can coordinate with other ligands;

[0020] Where L A It can bind to other ligands to include tridentate, tetradentate, pentadentate, or hexadentate ligands;

[0021] The condition is that when M is Ir, Z 1 It is BR C And Z 2 It is NR D When, then R A and from Z 1 R C They do not join together to form 5- or 6-membered rings, and originate from Z. 1 R C and from Z 2 R D They do not combine to form 5- or 6-membered rings;

[0022] and

[0023] At least one of the following eleven conditions is true:

[0024] 1) Structural part A is a 6- to 10-member ring, and X 5 R on B and from Z 2 R D Joining to form a multi-ring fused ring system, and X 4 Not N;

[0025] 2) Structural part A is a 5-membered ring, Z 2 It is NR D X 5 R on B and from Z 2 R D Joining to form a multi-ring fused ring system, and X 4 It's not N, the condition is if Z 1 It is BR C Then structural part A is imidazole, and X 1 and X 3 If it is N, then by R B and from Z 2 R DThe resulting polycyclic fused ring system is neither tetrahydroquinoline nor unsubstituted carbazole;

[0026] 3) M is Pt or Pd, and the structural part A is a 6-membered ring;

[0027] 4) Structural part A is a 6-membered ring, X 3 It is N, and Z 1 Selected from BR C GaR C SiR C R C’ and GeR C R C’ ;

[0028] 5) Structural part B is a 6-membered ring, X 4 It is N, and Z 1 Selected from BR C GaR C SiR C R C’ and GeR C R C’ The condition is that if Z 2 It is NR D Then R D and from X 5 R B Non-jointing forms a ring;

[0029] 6) Both structural part A and structural part B are 6-membered rings, Z 1 Selected from C=O, C=S, and C=Se, and Z 2 It is NR D The condition is that if M is Ir, then R D It is a cyclic group;

[0030] 7) R A R B R C (If it exists) and R D At least one of them (if present) includes a group selected from germanyl, boranyl and partially or fully deuterated silyl groups;

[0031] 8) R A R B R C (If it exists) and R D At least one of them (if it exists) includes three 6-membered aromatic rings that are not fused together with each other, or an aromatic ring fused with a non-aromatic ring.

[0032] 9) Structural part A is a 5-membered ring and Z 1 Selected from C=O, C=S, and C=Se; and

[0033] 10) M is Pt or Pd, X 1 and X 3 Both are N, X 2 It is C, and structural part A is an imidazole ring, and the two Rs A Joining to form a further substituted benzene ring; and

[0034] 11) The compound contains The structure and at least one of the following three conditions is true: (i) at least one R B It is neither hydrogen nor CH3, (ii)X 5 To X 9 At least one of them is N, and (iii)R D It exists and is a heteroaromatic or contains at least one electron-withdrawing group, provided that X 5 To X 9 If both are C, then R C and R D Non-joint formation of a 6-membered ring and R D no or ;as well as

[0035] The compound described is not one of the following compounds:

[0036] , , , , , , , , , , ,or .

[0037] In another respect, this disclosure provides compositions of compounds as described herein.

[0038] In another aspect, this disclosure provides an OLED having an organic layer comprising the compounds described herein.

[0039] In another aspect, this disclosure provides a consumer product comprising an OLED having an organic layer comprising the compounds described herein. Attached Figure Description

[0040] Figure 1 An organic light-emitting device is shown.

[0041] Figure 2 An inverted organic light-emitting device without an independent electron transport layer is demonstrated. Detailed Implementation

[0042] A. Terminology

[0043] Unless otherwise specified, the following terms as used herein are defined as follows:

[0044] As used herein, "top" means furthest from the substrate, and "bottom" means closest to the substrate. When the first layer is described as being "placed" "above" the second layer, the first layer is placed further away from the substrate. Unless it is specified that the first layer "contacts" the second layer, other layers may exist between the first and second layers. For example, even if various organic layers exist between the cathode and anode, the cathode can still be described as being "placed" "above" the anode.

[0045] As used herein, “solution-handleable” means capable of being dissolved, dispersed or transported in and / or deposited from a liquid medium in the form of a solution or suspension.

[0046] As used herein, and as will generally be understood by those skilled in the art, if the first energy level is closer to the vacuum level, then the first "Highest Occupied Molecular Orbital" (HOMO) or "Lowest Unoccupied Molecular Orbital" (LUMO) level is "greater than" or "higher than" the second HOMO or LUMO level. Since ionization potential (IP) is measured as a negative energy relative to the vacuum level, a higher HOMO level corresponds to an IP with a smaller absolute value (less negative IP). Similarly, a higher LUMO level corresponds to an electron affinity (EA) with a smaller absolute value (less negative EA). On a conventional energy level diagram with the vacuum level at the top, the LUMO levels of a material are higher than the HOMO levels of the same material. "Higher" HOMO or LUMO levels appear to be closer to the top of this diagram than "lower" HOMO or LUMO levels.

[0047] As used herein, and as those skilled in the art will generally understand, if the first work function has a higher absolute value, then the first work function is “greater” or “higher” than the second work function. This is because the work function is typically measured as a negative number relative to the vacuum level, meaning that the “higher” work function is more negative. On a conventional energy level diagram with the vacuum level at the top, the “higher” work function is illustrated as being farther from the vacuum level in the downward direction. Therefore, the definitions of HOMO and LUMO levels follow different rules than those for the work function.

[0048] This document may describe light emission regions by referring to the color of the light emitted by layers, materials, areas, and devices. Generally, as used herein, an emitting region that produces a particular color of light may include one or more emitting layers disposed in a stacked manner on top of each other.

[0049] As used herein, “NIR,” “red,” “green,” “blue,” and “yellow” layers, materials, regions, or devices refer to layers, materials, regions, or devices that emit light in the wavelength ranges of approximately 700–1500 nm, 580–700 nm, 500–600 nm, 400–500 nm, and 540–600 nm, respectively, or layers, materials, regions, or devices that have the highest emission spectral peak in the corresponding wavelength regions. In some arrangements, individual regions, layers, materials, or devices may provide separate “deep blue” and “light blue” emissions. As used herein, a “deep blue” emission component refers to an emission whose peak emission wavelength is at least approximately 4 nm smaller than the peak emission wavelength of the “light blue” emission component. Typically, the peak emission wavelength of the “light blue” emission component is in the range of approximately 465–500 nm, and the peak emission wavelength of the “deep blue” emission component is in the range of approximately 400–470 nm, but these ranges may vary for some configurations.

[0050] In some arrangements, a color-changing layer is provided that converts, modifies, or alters the color of light emitted by another layer to emit light with a different wavelength. This color-changing layer can be tuned to shift the wavelength of light emitted by the other layer by a defined amount, such as by the difference between the wavelength of the emitted light and the wavelength of the resulting light. Generally, there are two types of color-changing layers: color filters that modify the spectrum by removing light of unwanted wavelengths, and color-changing layers that convert higher-energy photons into lower-energy ones. For example, a "red" filter may be present to filter input light to remove light with wavelengths outside the approximately 580-700 nm range. The component of "color" refers to the component of light that produces or otherwise emits a particular color as described above when activated or used. For example, "a first emission region of a first color" and "a second emission region of a second color different from the first color" describe two emission regions that emit two different colors as described above when activated within the device.

[0051] As used herein, the light initially generated by a material, layer, or region is the exact opposite of the light ultimately emitted by the same or different structures, allowing the emitting materials, layers, and regions to be distinguished from each other and from other structures. Initial light generation is typically a result of energy level changes that lead to photon emission. For example, an organic emitting material may initially produce blue light, which can be converted into red or green light by a color filter, quantum dot, or other structure, causing the entire emitting stack or subpixel to emit red or green light. In this case, the initial emitting material, region, or layer may be referred to as the "blue" component, even if the subpixel is the "red" or "green" component.

[0052] In some cases, the color of components, such as the color of emitting regions, subpixels, color-changing layers, etc., can preferably be described according to 1931 CIE coordinates. For example, a yellow emitting material may have multiple peak emission wavelengths, one in or near the edge of the "green" region and one in or near the edge of the "red" region, as previously described. Therefore, as used herein, each color item also corresponds to a shape in the 1931 CIE coordinate color space. The shape in the 1931 CIE color space is constructed by tracing the trajectory between two color points and any other interior points. For example, the interior shape parameters for red, green, blue, and yellow can be defined as follows:

[0053]

[0054] The terms “halogen,” “halogen,” and “halogen group” are used interchangeably and refer to fluorine, chlorine, bromine, and iodine.

[0055] The term "acyl" refers to a substituted carbonyl group (-C(O)-R). s ).

[0056] The term "ester" refers to a substituted oxycarbonyl group (-OC(O)-R). s or -C(O)-OR s ) group.

[0057] The term "ether" refers to -OR s Group.

[0058] The terms "thio-" or "thioether" are used interchangeably and refer to -SR s Group.

[0059] The term "selenyl" refers to -SeR s Group.

[0060] The term "sulfinyl" refers to -S(O)-R s Group.

[0061] The term "sulfonyl" refers to -SO2-R s Group.

[0062] The term "phosphono" refers to a group containing at least one phosphorus atom bonded to the relevant structure. Common examples of phosphono groups include, but are not limited to, -P(R) s )2 group or -PO(R s )2 groups, wherein each R s They can be the same or different.

[0063] The term "silyl group" refers to a group containing at least one silicon atom bonded to the relevant structure. Common examples of silyl groups include, but are not limited to, -Si(R s )3 groups, wherein each R s They can be the same or different.

[0064] The term "germanium alkyl" refers to a group containing at least one germanium atom bonded to the relevant structure. Common examples of germanium alkyl groups include, but are not limited to, -Ge(R s )3 groups, wherein each R s They can be the same or different.

[0065] The term "boronyl" refers to a group containing at least one boron atom bonded to the relevant structure. Common examples of boronyl groups include, but are not limited to, -B(R s )2 group or its Lewis adduct -B(R s )3 groups, of which R s They can be the same or different.

[0066] In each of the above, R s It can be hydrogen or a substituent selected from the group of general substituents as defined in this application. Preferred R s Selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, and combinations thereof. More preferably, R s Choose from the following groups: alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0067] The term "alkyl" refers to and includes both straight-chain and branched alkyl groups having alkyl carbon atoms bonded to the relevant structure. Preferred alkyl groups are those containing one to fifteen carbon atoms, more preferably one to nine carbon atoms, and include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1,3-dimethylpropyl, 1,1-dimethylpropyl, 2-ethylpropyl, 1,2-dimethylpropyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, n-heptyl, 2-methylhexyl, 3-methylhexyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl, 3,3-dimethylpentyl, 3-ethylpentyl, 2,2,3-trimethylbutyl, etc. In addition, alkyl groups can be further substituted.

[0068] The term "cycloalkyl" refers to and includes monocyclic, polycyclic, and spirocyclic alkyl groups having cycloalkyl carbon atoms bonded to the relevant structure. Preferred cycloalkyl groups are those containing 3 to 12 cyclic carbon atoms and include cyclopropyl, cyclopentyl, cyclohexyl, bicyclo[3.1.1]heptyl, spiro[4.5]decyl, spiro[5.5]undecyl, adamantyl, etc. Furthermore, the cycloalkyl group may be further substituted.

[0069] The terms "heteroalkyl" or "heterocyclic alkyl" refer to an alkyl or cycloalkyl group having at least one carbon atom substituted with a heteroatom. Optionally, the at least one heteroatom is selected from O, S, N, P, B, Si, Ge, and Se, preferably O, S, or N. Furthermore, the heteroalkyl or heterocyclic alkyl group may be further substituted.

[0070] The term "alkenyl" refers to and includes both straight-chain and branched olefin groups. An alkenyl is essentially an alkyl group comprising at least one carbon-carbon double bond in an alkyl chain, wherein one carbon atom originates from a carbon-carbon double bond bonded to the associated structure. A cycloalkenyl is essentially a cycloalkyl group comprising at least one carbon-carbon double bond in a cycloalkyl ring. As used herein, the term "heteroalkenyl" refers to an alkenyl group having at least one carbon atom substituted by a heteroatom. Optionally, the at least one heteroatom is selected from O, S, N, P, B, Si, Ge, and Se, preferably O, S, or N. Preferred alkenyl, cycloalkenyl, or heteroalkenyl groups are those containing two to fifteen carbon atoms. Furthermore, alkenyl, cycloalkenyl, or heteroalkenyl groups may be further substituted.

[0071] The term "alkynyl" refers to and includes both straight-chain and branched alkyne groups. An alkynyl group is essentially an alkyl group comprising at least one carbon-carbon triple bond in an alkyl chain, where one carbon atom originates from a carbon-carbon triple bond bonded to the relevant structure. Preferred alkynyl groups are those containing two to fifteen carbon atoms. Furthermore, the alkynyl group may be further substituted.

[0072] The terms "aralkyl" or "arylalkyl" are used interchangeably and refer to an aryl-substituted alkyl group having an alkyl carbon atom bonded to the relevant structure. Furthermore, aralkyl groups may be further substituted.

[0073] The term "heterocyclic group" refers to and includes aromatic and non-aromatic cyclic groups containing at least one heteroatom. Optionally, the at least one heteroatom is selected from O, S, Se, N, P, B, Si, Ge, and Se, preferably O, S, N, or B. Heteroaromatic cyclic groups can be used interchangeably with heteroaryl groups. Preferred non-aromatic heterocyclic groups are non-aromatic heterocyclic groups containing 3 to 10 ring atoms, preferably non-aromatic heterocyclic groups containing 3 to 7 ring atoms including at least one heteroatom, and include cyclic amines such as morpholino, piperidinyl, pyrrolyl, etc., and cyclic ethers / thioethers such as tetrahydrofuran, tetrahydropyran, tetrahydrothiophene, etc. Furthermore, the heterocyclic group may be further substituted or fused.

[0074] The term "aryl" refers to and includes both monocyclic and polycyclic aromatic hydrocarbon groups. A polycyclic aromatic hydrocarbon can have two or more rings, wherein two carbons are common to two adjacent rings (the rings are "fused"). Preferred aryl groups are those containing six to thirty carbon atoms, preferably six to twenty-four carbon atoms, six to eighteen carbon atoms, and more preferably six to twelve carbon atoms. Particularly preferred are aryl groups having six, ten, twelve, fourteen, or eighteen carbon atoms. Suitable aryl groups include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenanthrene, pyrene, β-carotene, perylene, and azulene, preferably phenyl, biphenyl, terphenyl, triphenylene, and naphthalene. Furthermore, aryl groups can be further substituted or fused, such as, but not limited to, fluorene.

[0075] The term "heteroaryl" refers to and includes both monocyclic aromatic groups and polycyclic aromatic ring systems having at least one heteroatom. Heteroatoms include, but are not limited to, O, S, Se, N, P, B, Si, Ge, and Se. In many cases, O, S, N, or B are preferred heteroatoms. Monocyclic heteroaromatic systems are preferably monocyclic rings having 5 or 6 ring atoms, and the rings may have one to six heteroatoms. Polycyclic heterocyclic systems may have two or more aromatic rings, wherein two atoms are common to two adjacent rings (the rings are "fused"), and at least one of the rings is a heteroaryl. Polycyclic heteroaromatic ring systems may have one to six heteroatoms in each ring. Preferred heteroaryls are those containing three to thirty carbon atoms, preferably three to twenty-four carbon atoms, three to eighteen carbon atoms, and more preferably three to twelve carbon atoms. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenene, furan, thiophene, benzofuran, benzothiophene, benzoselenene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxtriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxthiazine, oxadiazine, indole, benzimidazole, Indazole, indoxazine, benzoxazole, benzoisoxazole, benzothiazole, quinoline, isoquinoline, cinnamoline, quinazoline, quinoxaline, naphthidine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuranopyridine, furanodipyridine, benzothiophenopyridine, thiophenodipyridine, benzoselenophenopyridine, selenophenodipyridine, aziborane, cycloborane, 5λ 2 ,9λ 2 -diaza-13b-boronanaphene[2,3,4-de]anthracene, 5λ 2 -Benzo[d]benzo[4,5]imidazo[3,2-a]imidazolium and 5,9-dioxa-13b-boronazona[3,2,1-de]anthracene; preferably dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazolium, pyridine, triazine, benzimidazole, 5λ 2 ,9λ 2 -diaza-13b-boronanaphene[2,3,4-de]anthracene, 5λ 2 -Benzo[d]benzo[4,5]imidazo[3,2-a]imidazo[3,2-a]imidazo[3,2,1-de]anthracene. Additionally, heteroaryl groups can be further substituted or fused.

[0076] Among the aryl and heteroaryl groups listed above, triphenylene, naphthalene, anthracene, dibenzothiophene, dibenzofuran, dibenzoselenene, carbazole, indolocarbazole, imidazole, pyridine, pyrazine, pyrimidine, triazine, benzimidazole, and 5λ are included. 2 ,9λ 2-diaza-13b-boronanaphene[2,3,4-de]anthracene, 5λ 2 -Benzo[d]benzo[4,5]imidazo[3,2-a]imidazo, 5,9-dioxa-13b-boronazona[3,2,1-de]anthracene groups, and their corresponding aza analogs are of particular interest.

[0077] In many cases, the general substituents are selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silalkyl, germanalkyl, boranalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, selenalkyl, sulfinyl, sulfonyl, phosphin, and combinations thereof.

[0078] In some cases, the preferred general substituents are selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silalkyl, germanalkyl, boroalkyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thioyl, and combinations thereof.

[0079] In some cases, more preferred general substituents are selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, alkoxy, aryloxy, amino, silyl, germanyl, boronyl, aryl, heteroaryl, nitrile, thio, and combinations thereof.

[0080] In some cases, even more preferred general substituents are selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, silyl, aryl, heteroaryl, nitriles and combinations thereof.

[0081] In other cases, the most preferred general substituent is selected from the group consisting of: deuterium, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0082] In the absence of a specific definition of one or more substituents (e.g., R, R', R", R), A R A R 1 In the case of R1, etc., each of the one or more substituents should be understood to independently represent hydrogen or a substituent selected from the group consisting of general substituents as defined herein. Similarly, each of the one or more substituents may optionally be coupled or fused with another substituent to form a ring. It should also be understood that any substituent selected from general substituents as defined herein may also be selected from preferred general substituents as defined herein, more preferred general substituents as defined herein, even more preferred general substituents as defined herein, or most preferred general substituents as defined herein.

[0083] The terms "substituted" and "substituted" refer to substituents other than H being bonded to the relevant position, such as carbon or nitrogen. For example, when R... 1 When representing monosubstitution, then an R 1 It must not be H (i.e., substitution). Similarly, when R 1 When representing disubstituted substitution, then the two Rs 1 It must not be H. Similarly, when R... 1 When R represents zero or no substitution, 1 For example, it could be hydrogen atoms with all available valences in the ring atom, such as carbon atoms in benzene and nitrogen atoms in pyrrole, or simply none for ring atoms with fully saturated valences, such as nitrogen atoms in pyridine. The maximum possible number of substitutions in a ring structure will depend on the total number of available valences in the ring atoms.

[0084] As used herein, “combination thereof” means that one or more members of the applicable list are combined to form a known or chemically stable arrangement that can be conceived by one of ordinary skill in the art from the applicable list. For example, alkyl and deuterium can be combined to form partially or fully deuterated alkyl groups; halogen and alkyl groups can be combined to form haloalkyl substituents; and halogen, alkyl, and aryl groups can be combined to form haloaralkyl groups. In one instance, the term substitution includes a combination of two to four listed groups. In another instance, the term substitution includes a combination of two to three groups. In yet another instance, the term substitution includes a combination of two groups. Preferred combinations of substituents are combinations containing up to fifty atoms that are not hydrogen or deuterium, or combinations containing up to forty atoms that are not hydrogen or deuterium, or combinations containing up to thirty atoms that are not hydrogen or deuterium. In many cases, preferred combinations of substituents will include up to twenty atoms that are not hydrogen or deuterium.

[0085] The term "aza" in the phrases used herein, namely aza-dibenzofuran, aza-dibenzothiophene, etc., implies that one or more of the CH groups in the corresponding aromatic ring can be substituted with nitrogen atoms. For example, and without limitation, azatriphenylene covers dibenzo[f,h]quinoxaline and dibenzo[f,h]quinoline. Other nitrogen analogs of the aza-derived compounds described above will be readily contemplated by those skilled in the art, and all such analogs are intended to be covered by the terminology set forth herein.

[0086] This disclosure includes all compounds of this disclosure with acceptable isotopic labeling, wherein one or more atoms are replaced by atoms having the same atomic number but with an atomic mass or mass number different from those normally found in nature.

[0087] Examples of suitable isotopes to be included in compounds of this disclosure include isotopes of hydrogen, for example... 2 H and 3 H; isotopes of carbon, such as11 C 13 C and 14 C; isotopes of chlorine, for example 36 Cl; isotopes of fluorine, for example 18 F; Isotopes of iodine, for example 123 I, 124 I and 125 I; Isotopes of nitrogen, such as 13 N and 15 N; isotopes of oxygen, such as 15 O、 17 O and 18 O; isotopes of phosphorus, such as 32 P; and isotopes of sulfur, such as 35 S.

[0088] Certain isotopically labeled compounds disclosed herein, such as those doped with radioactive isotopes, can be used in diagnostics and other research. Radioactive isotope tritium (i.e., 3 H) and carbon-14 (i.e. 14 C) It is particularly suitable for this purpose due to its ease of incorporation and convenient detection methods.

[0089] Using heavier isotopes such as deuterium (i.e., 2 H) replacement can provide some advantages resulting from greater stability, and may therefore be preferred in some cases.

[0090] The isotopically labeled compounds of the present invention can generally be prepared by conventional techniques known to those skilled in the art or by methods similar to those described in the appended examples and preparations, using a suitable isotopically labeled reagent instead of the previously used unlabeled reagent.

[0091] For example, deuterated compounds can be readily prepared using methods known in the art. For instance, U.S. Patent No. 8,557,400, Patent Publication No. WO 2006 / 095951, and U.S. Patent Application Publication No. US 2011 / 0037057 (which are incorporated herein by reference in their entirety) describe the preparation of deuterated organometallic complexes. Further references to Ming Yan et al., Tetrahedron 2015, 71, 1425-30, and Atzrodt et al., Angewandte Chemie International Edition (Review) 2007, 46, 7744-65 (which are incorporated herein by reference in their entirety) describe efficient methods for the deuteration of methylene hydrogen in benzylamines and the replacement of aromatic cyclic hydrogens with deuterium, respectively.

[0092] As used herein, any specifically listed substituent, such as, but not limited to, methyl, phenyl, pyridyl, etc., includes its undeuterated, partially deuterated, and fully deuterated forms. Similarly, substituents, such as, but not limited to, alkyl, aryl, cycloalkyl, heteroaryl, etc., also include their undeuterated, partially deuterated, and fully deuterated forms. Unless otherwise specified, atoms in a chemical structure that are not completely filled with H or D should be considered to include their undeuterated, partially deuterated, and fully deuterated forms. For example, chemical structures This means including C6H6, C6D6, C6H3D3, and any other partially deuterated variants thereof. Some common basic partially or fully deuterated groups include, but are not limited to, CD3, CD2C(CH3)3, C(CD3)3, and C6D5. Similarly, where the partially or fully defined atomic structure indicates that a particular position can be deuterated, it is also conceivable to have the same atomic structure with one, two, or at most all deuterated atoms replaced by hydrogen.

[0093] It should be understood that when a molecular fragment is described as a substituent or additionally linked to another part, its name can be written as if it were a fragment (e.g., phenyl, phenylene, naphthyl, dibenzofuranyl) or as if it were a whole molecule (e.g., benzene, naphthalene, dibenzofuran). As used herein, these different ways of naming substituents or linked fragments are considered equivalent.

[0094] In some cases, a pair of substituents in a molecule can join or fuse to form a ring. Preferred rings are five- to nine-membered carbon rings or heterocycles, including both cases where the ring formed by the pair of substituents is partially saturated and cases where the ring formed by the pair of substituents is partially unsaturated. In other cases, a pair of adjacent substituents can join or fuse to form a ring. As used herein, “adjacent” means that the two substituents involved can be adjacent to each other on the same ring, or on two neighboring rings having two closest available substituted positions (such as the 2, 2' positions in biphenyl or the 1, 8 positions in naphthalene).

[0095] B. Compounds disclosed herein

[0096] In one aspect, this disclosure provides a compound having a first ligand L comprising the structure of formula I. A :

[0097] , Formula I;

[0098] Structural parts A and B are each independently a single-ring ring or a multi-ring fused ring system, wherein each ring in the single-ring ring or multi-ring fused ring system is independently a 5- to 10-membered carbon ring or heterocyclic ring.

[0099] Where K 1 and K 2Each is independently selected from direct bonds, O, S, N(R) α ), P(R α ), B(R) α ), C(R α (R) β ) and Si(R α (R) β );

[0100] Z 1 Selected from BR C C=O, C=S, C=Se, GaR C SiR C R C′ and GeR C R C′ ;

[0101] Z 2 Selected from NR D O and S;

[0102] Where X 1 To X 5 Each can be independently represented as C or N;

[0103] Where R A and R B Each can be independently represented as a single substitution up to the maximum permissible substitution or no substitution;

[0104] Where R α R β R A R B R C R C’ and R D Independently hydrogen or a substituent selected from the following: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silalkyl, germanalkyl, boronalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphinyl, boronyl, selenyl, and combinations thereof;

[0105] Where R α R β R A R B R C R C’ and R D Any two elements can be connected or fused to form a ring;

[0106] in Is it a single bond or a double bond?

[0107] Where L AFit to metal M;

[0108] Metal M can coordinate with other ligands;

[0109] Where L A It can bind to other ligands to include tridentate, tetradentate, pentadentate or hexadentate ligands.

[0110] In some implementations, when M is Ir, Z 1 It is BR C And Z 2 It is NR D When, then R A and from Z 1 R C They do not join together to form 5- or 6-membered rings, and originate from Z. 1 R C and from Z 2 R D They do not combine to form 5- or 6-membered rings;

[0111] In some implementations, at least one of the following eleven conditions is true:

[0112] 1) Structural part A is a 6- to 10-member ring, and X 5 R on B and from Z 2 R D Joining to form a multi-ring fused ring system, and X 4 Not N;

[0113] 2) Structural part A is a 5-membered ring, Z 2 It is NR D X 5 R on B and from Z 2 R D Joining to form a multi-ring fused ring system, and X 4 It's not N, the condition is if Z 1 It is BR C Structural part A is imidazole, and X 1 and X 3 If it is N, then by R B and from Z 2 R D The resulting polycyclic fused ring system is neither tetrahydroquinoline nor unsubstituted carbazole;

[0114] 3) M is Pt or Pd, and the structural part A is a 6-membered ring;

[0115] 4) Structural part A is a 6-membered ring, X 3 It is N, Z 1 Selected from BR CGaR C SiR C R C’ and GeR C R C’ ;

[0116] 5) Structural part B is a 6-membered ring, X 4 It is N, Z 1 Selected from BR C GaR C SiR C R C’ and GeR C R C’ The condition is that if Z 2 It is NR D Then R D and from X 5 R B Non-jointing forms a ring;

[0117] 6) Both structural part A and structural part B are 6-membered rings, Z 1 Selected from C=O, C=S, and C=Se, and Z 2 It is NR D The condition is that if M is Ir, then R D It is a cyclic group;

[0118] 7) R A R B R C (If it exists) and R D At least one of them (if present) includes a group selected from germanyl, boranyl and partially or fully deuterated silyl groups;

[0119] 8) R A R B R C (If it exists) and R D At least one of them (if it exists) includes three 6-membered aromatic rings that are not fused together with each other, or an aromatic ring fused with a non-aromatic ring.

[0120] 9) Structural part A is a 5-membered ring and Z 1 Selected from C=O, C=S, and C=Se;

[0121] 10) M is Pt or Pd, X 1 and X 3 Both are N, X 2 It is C, structural part A is an imidazole ring, and the two Rs A Joining to form a further substituted benzene ring; and

[0122] 11) The compound contains The structure and at least one of the following three conditions is true: (i) at least one R B It is neither hydrogen nor CH3, (ii)X 5 To X 9 At least one of them is N, and (iii)R D It exists and is a heteroaryl group or contains at least one electron-withdrawing group, provided that X 5 To X 9 If both are C, then R C and R D Non-joint formation of a 6-membered ring and R D no or In some implementations, at least one of conditions 10) and 11) is true. In some implementations, one of conditions 10) and 11) is true.

[0123] In some embodiments, the compound is not one of the following compounds:

[0124] , , , , , , , , , , ,and .

[0125] In some implementations, the first ligand L A It is basically composed of formula I.

[0126] In some implementations, the first ligand L A It has the structure of Formula I.

[0127] In some embodiments, any two substituents can join or fuse to form a ring. In some embodiments, R α R β R A R B R C and R D At least two of them are alkyl groups and are joined to form a ring, which can be further substituted. In some embodiments, at least two R... A The coupling forms a ring. In some embodiments, at least two R... B The coupling forms a ring. In some embodiments, at least one R A With an R C The coupling forms a ring. In some embodiments, at least one R D With an RB The coupling forms a ring. In some embodiments, at least one R α With an R A The coupling forms a ring. In some embodiments, at least one R β With an R A The coupling forms a ring. In some embodiments, at least one R α With an R B The coupling forms a ring. In some embodiments, at least one R β With an R B The ring is formed by bonding. In some of the above embodiments, the ring formed by the two substituents can be an aromatic ring or a non-aromatic ring. In some of these embodiments, the non-aromatic ring can be formed by two alkyl substituents.

[0128] In some implementations, the first ligand L A Having the structure of Formula I, at least one R α R β R A R B R C R C’ and R D It is partially or completely deuterated. In some embodiments, at least one R A It is partially or completely deuterated. In some embodiments, at least one R B It is partially or completely deuterated. In some embodiments, at least one R C It is partially or completely deuterated. In some embodiments, at least one R C’ It is partially or completely deuterated. In some embodiments, at least one R D It is partially or completely deuterated. In some embodiments, at least one R α Or R β It is partially or completely deuterated.

[0129] In some implementations, the first ligand L A Having the structure of Formula I, at least one R A R B R C R C’ Or R D Selected from general substituents as defined herein. In some embodiments, at least one R A Selected from generic substituents as defined herein. In some embodiments, at least one R B Selected from generic substituents as defined herein. In some embodiments, at least one R CSelected from generic substituents as defined herein. In some embodiments, at least one R C’ Selected from generic substituents as defined herein. In some embodiments, at least one R D Selected from universal substituents as defined in this article.

[0130] In some implementations, the first ligand L A Having the structure of Formula I, at least one R A R B R C R C’ Or R D The preferred general substituents are selected from those defined herein. In some embodiments, at least one R A Selected from preferred general substituents as defined herein. In some embodiments, at least one R B Selected from preferred general substituents as defined herein. In some embodiments, at least one R C Selected from preferred general substituents as defined herein. In some embodiments, at least one R C’ Selected from preferred general substituents as defined herein. In some embodiments, at least one R D Selected from preferred general substituents as defined herein.

[0131] In some implementations, the first ligand L A Electron-withdrawing groups comprising structures selected from the following EWG1 list: F, CF3, CN, COCH3, CHO, COCF3, COOMe, COOCF3, NO2, SF3, SiF3, PF4, SF5, OCF3, SCF3, SeCF3, SOCF3, SeOCF3, SO2F, SO2CF3, SeO2CF3, OSeO2CF3, OCN, SCN, SeCN, NC. + N(R k2 )3, (R k2 )2CCN,(R k2 )2CCF3, CNC(CF3)2, BR k3 R k2Substituted or unsubstituted dibenzoboranecyclopentadiene, 1-substituted carbazole, 1,9-substituted carbazole, substituted or unsubstituted carbazole, substituted or unsubstituted pyridine, substituted or unsubstituted pyrimidine, substituted or unsubstituted pyrazine, substituted or unsubstituted pyridoxine, substituted or unsubstituted triazine, substituted or unsubstituted oxazole, substituted or unsubstituted benzoxazole, substituted or unsubstituted thiazole, substituted or unsubstituted benzothiazole, substituted or unsubstituted imidazole, substituted or unsubstituted benzimidazole, ketone, carboxylic acid, ester, nitrile, isonitrile, sulfinyl, sulfonyl, partially and fully fluorinated alkyl, partially and fully fluorinated aryl, partially and fully fluorinated heteroaryl, cyano-containing alkyl, cyano-containing aryl, cyano-containing heteroaryl, isocyanate. , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , and ;

[0132] Each Rk1 This indicates single substitution up to the maximum permissible substitution, or no substitution at all;

[0133] Where Y G Selected from BR e NR e PR e ,O,S,Se,C=O,S=O,SO2,CR e R f SiR e R f and G e R e R f’ ;as well as

[0134] Where R k1 R k2 R k3 R e and R f Each of them is independently hydrogen or a substituent selected from the generic substituents as defined herein.

[0135] In some implementations, the first ligand L A Includes electron-withdrawing groups from the group consisting of structures selected from the following EWG2 LIST:

[0136] , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , ,and .

[0137] In some implementations, the first ligand L A Includes electron-withdrawing groups selected from the group consisting of structures in the following EWG3 LIST:

[0138] , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , and .

[0139] In some implementations, the first ligand L A Includes electron-withdrawing groups from the group consisting of structures selected from the following EWG4 LIST:

[0140] , , , , , , , , , , , , , , , , , , , , , , , , and .

[0141] In some implementations, the first ligand L A Containing π-electron-deficient electron-withdrawing groups, selected from the group consisting of structures in the following Pi-EWG list: CN, COCH3, CHO, COCF3, COOMe, COOCF3, NO2, SF3, SiF3, PF4, SF5, OCF3, SCF3, SeCF3, SOCF3, SeOCF3, SO2F, SO2CF3, SeO2CF3, OSeO2CF3, OCN, SCN, SeCN, NC. + N(R k2 )3, BR k2 R k3Substituted or unsubstituted dibenzoboranecyclopentadiene, 1-substituted carbazole, 1,9-substituted carbazole, substituted or unsubstituted carbazole, substituted or unsubstituted pyridine, substituted or unsubstituted pyrimidine, substituted or unsubstituted pyrazine, substituted or unsubstituted pyridazine, substituted or unsubstituted triazine, substituted or unsubstituted oxazole, substituted or unsubstituted benzoxazole, substituted or unsubstituted thiazole, substituted or unsubstituted benzothiazole, substituted or unsubstituted imidazole, substituted or unsubstituted benzimidazole, ketone, carboxylic acid, ester, nitrile, isonitrile, sulfinyl, sulfonyl, partially and fully fluorinated aryl, partially and fully fluorinated heteroaryl, cyano-containing aryl, cyano-containing heteroaryl, isocyanate. , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , and The variants are the same as those previously defined.

[0142] In some implementations, the first ligand L A Having the structure of Formula I, at least one R A It is or contains an electron-withdrawing group from an EWG1 LIST as defined herein. In some embodiments, at least one R A It is or contains an electron-withdrawing group from EWG2 LIST as defined herein. In some embodiments, at least one R A It is or contains an electron-withdrawing group from EWG3 LIST as defined herein. In some embodiments, at least one RA It is or contains an electron-withdrawing group from EWG4 LIST as defined herein. In some embodiments, at least one R A It is or contains electron-withdrawing groups from Pi-EWG LIST as defined herein.

[0143] In some implementations, the first ligand L A Having the structure of Formula I, at least one R B It is or contains an electron-withdrawing group from an EWG1 LIST as defined herein. In some embodiments, at least one R B It is or contains an electron-withdrawing group from EWG2 LIST as defined herein. In some embodiments, at least one R B It is or contains an electron-withdrawing group from EWG3 LIST as defined herein. In some embodiments, at least one R B It is or contains an electron-withdrawing group from EWG4 LIST as defined herein. In some embodiments, at least one R B It is or contains electron-withdrawing groups from Pi-EWG LIST as defined herein.

[0144] In some implementations, the first ligand L A Having the structure of Formula I, at least one R C It is or contains an electron-withdrawing group from an EWG1 LIST as defined herein. In some embodiments, at least one R C It is or contains an electron-withdrawing group from EWG2 LIST as defined herein. In some embodiments, at least one R C It is or contains an electron-withdrawing group from EWG3 LIST as defined herein. In some embodiments, at least one R C It is or contains an electron-withdrawing group from EWG4 LIST as defined herein. In some embodiments, at least one R C It is or contains electron-withdrawing groups from Pi-EWG LIST as defined herein.

[0145] In some implementations, the first ligand L A Having the structure of Formula I, at least one R C’ It is or contains an electron-withdrawing group from an EWG1 LIST as defined herein. In some embodiments, at least one R C’ It is or contains an electron-withdrawing group from EWG2 LIST as defined herein. In some embodiments, at least one R C’ It is or contains an electron-withdrawing group from EWG3 LIST as defined herein. In some embodiments, at least one RC’ It is or contains an electron-withdrawing group from EWG4 LIST as defined herein. In some embodiments, at least one R C’ It is or contains electron-withdrawing groups from Pi-EWG LIST as defined herein.

[0146] In some implementations, the first ligand L A Having the structure of Formula I, at least one R D It is or contains an electron-withdrawing group from an EWG1 LIST as defined herein. In some embodiments, at least one R D It is or contains an electron-withdrawing group from EWG2 LIST as defined herein. In some embodiments, at least one R D It is or contains an electron-withdrawing group from EWG3 LIST as defined herein. In some embodiments, at least one R D It is or contains an electron-withdrawing group from EWG4 LIST as defined herein. In some embodiments, at least one R D It is or contains electron-withdrawing groups from Pi-EWG LIST as defined herein.

[0147] In some implementations, when M is Ir, Z 1 It is BR C And Z 2 It is NR D At that time, R A and from Z 1 R C They do not join together to form 5- or 6-membered rings, and originate from Z. 1 R C and from Z 2 R D They do not combine to form 5- or 6-membered rings.

[0148] In some implementations, structural part A is a 6- to 10-member ring, and X 5 R on B and Z 2 R on D Joining to form a multi-ring fused ring system, and X 4 Not N. In some embodiments, structural part A is a 6-membered ring. In some embodiments, structural part A is a pyridine or pyrimidine ring. In some embodiments, structural part A is a pyridine ring. In some embodiments, X 5 R on B and Z 2 R on D The coupling forms a polycyclic fused ring system comprising two fused rings. In some embodiments, X 5 R onB and from Z 2 R D It is conjugated with ring B to form substituted or unsubstituted carbazole. In some embodiments, X 5 R on B and from Z 2 R D It is combined with ring B to form a substituted carbazole. In some embodiments, X 5 R on B and from Z 2 R D Together with ring B, it is bonded to form a substituted polycyclic fused ring system with EWG. In some embodiments, X 5 R on B and from Z 2 R D It combines with ring B to form a substituted polycyclic fused ring system with CN substituted. In some embodiments, X 5 R on B and from Z 2 R D It combines with ring B to form carbazole fused with one or more other rings.

[0149] In some implementations, structural part A is a 5-membered ring, Z 2 It is NR D X 5 R on B and from Z 2 R D Joining to form a multi-ring fused ring system, and X 4 It's not N, the condition is if Z 1 It is BR C Structural part A is imidazole, and X 1 and X 3 If it is N, then by R B and from Z 2 R D The resulting polycyclic fused ring system is not tetrahydroquinoline or unsubstituted carbazole. In some embodiments, structural moiety A is imidazole, pyrrole, pyrazole, or triazole. In some embodiments, structural moiety A is preferably imidazole. In some embodiments, the two R... A The rings are joined to form a monocyclic or polycyclic ring system fused to structural portion A. In some embodiments, structural portion A is benzimidazole. In some embodiments, X 5 R on B and from Z 2 R D It combines with ring B to form a substituted carbazole. In some embodiments, X 5 R on Band from Z 2 R D Together with ring B, they form a multi-ring fused ring system replacing EWG. In some embodiments, X 5 R on B and from Z 2 R D Together with ring B, they form a polycyclic fused ring system in which CN is substituted. In some embodiments, X 5 R on B and from Z 2 R D Together with ring B, it forms a carbazole fused with one or more additional rings. In some embodiments, M is Pt or Pd, and structural moiety A is a 6-membered ring. In some embodiments, M is Pt. In some embodiments, structural moiety A is pyridine or pyrimidine. In some embodiments, structural moiety A is pyridine.

[0150] In some implementations, structural part A is a 6-membered ring, X 3 It is N, and Z 1 Selected from BR C GaR C SiR C R C’ and GeR C R C’ In some embodiments, structural moiety A is pyridine or pyrimidine. In some embodiments, structural moiety A is pyridine. In some embodiments, Z... 1 It is BR C or SiR C R C’ In some implementation schemes, Z 1 It is BR C .

[0151] In some implementations, structural part A and structural part B are both 6-membered rings, Z 1 Selected from C=O, C=S, and C=Se, and Z 2 It is NR D The condition is that if M is Ir, then R D It is a cyclic group.

[0152] In some implementations, structural part B is a 6-membered ring, X 4 It is N, and Z 1 Selected from BR C GaR C SiR C R C’ and GeR C R C’ The condition is that if Z 2 It is NRD Then R D and from X 5 R B Non-bonding ring formation. In some embodiments, structural moiety B is pyridine or pyrimidine. In some embodiments, structural moiety B is pyridine. In some embodiments, Z... 1 It is BR C or SiR C R C’ In some implementation schemes, Z 1 It is BR C In some implementation schemes, Z 2 It is NR D In some implementations, R C With R A They are joined to form single-ring or multi-ring fused ring systems. In some embodiments, R C Not with R A They join together to form a ring.

[0153] In some implementations, structural part A and structural part B are both 6-membered rings, Z 1 Selected from C=O, C=S, and C=Se, and Z 2 It is NR D The condition is that if M is Ir, then R D It is a cyclic group. In some embodiments, Z 1 It is C=O. In some implementations, R D It is a substituted or unsubstituted aryl or heteroaryl group. In some embodiments, R D It is a substituted or unsubstituted phenyl ring. In some embodiments, R D It is an alkyl-substituted aryl group.

[0154] In some implementation schemes, R A R B R C (If it exists) and R D At least one of them (if present) contains a group selected from germanyl, boranyl, and partially or fully deuterated silyl groups. In some embodiments, R A R B R C and R D One of them contains a boron alkyl group. In some embodiments, R B Contains a boron alkyl group. In some embodiments, Z 2 It is NR D And R D Joined to at least one R B To form a ring containing a boron alkyl group. In some embodiments, R A RB R C and R D One of them contains a silyl or germanyl group. In some embodiments, R A R B R C and R D One of them contains a trialkylgermanyl group. In some embodiments, R A R B R C and R D One of them contains a fully or partially deuterated trialkylsilyl group. In some embodiments, R A R B R C and R D One of them contains a silane, which contains a fully or partially deuterated aromatic ring.

[0155] In some implementation schemes, R A R B R C (If it exists) and R D At least one of them (if present) comprises three non-fused 6-membered aromatic rings, or aromatic rings fused with non-aromatic rings. In some embodiments, R A R B R C (If it exists) and R D At least one of them (if present) contains a substituted or unsubstituted triphenyl group. In some embodiments, R A R B R C (If it exists) and R D At least one of them (if present) comprises an alkyl-substituted terphenyl. In some embodiments, R A R B R C (If it exists) and R D At least one of them (if present) contains an aromatic ring fused with a saturated 5- or 6-membered carbon ring. In some embodiments, R A R B R C (If it exists) and R D At least one of them (if present) contains a phenyl ring fused with a saturated 6-membered carbon ring.

[0156] In some implementations, structural part A is a 5-membered ring, and Z... 1The fraction is selected from C=O, C=S, and C=Se. In some embodiments, structural part A is selected from imidazole, pyrrole, triazole, oxazole, and furan. In some embodiments, structural part A is imidazole. In some embodiments, Z... 1 It is C=O.

[0157] In some implementations, M is Pt or Pd, X 1 and X 3 Both are N, X 2 It is C, structural part A is an imidazole ring, and the two Rs A The compounds are joined to form a benzene ring, which is further substituted. In some embodiments, the benzene ring is substituted with deuterium, aryl, heteroaryl, alkyl, silyl, or combinations thereof. In some embodiments, the benzene ring is substituted with an alkyl group.

[0158] In some embodiments, the compound comprises The structure and at least one of the following three conditions is true: (i) at least one R B It is neither hydrogen nor CH3, (ii)X 5 To X 9 At least one of them is N, and (iii)R D It exists and is a heteroaryl group or contains at least one electron-withdrawing group, provided that X 5 To X 9 If both are C, then R C and R D Non-joint formation of a 6-membered ring and R D no or In some implementation schemes, Z 1 It is BR and Z 2 It is NR. In some implementations, Z 1 It is C=O and Z 2 It is NR.

[0159] In some implementations, structural part A is a 5-membered ring, and Z... 1 Selected from C=O, C=S, and C=Se.

[0160] In some implementation schemes, Z 2 It is NR D R D It includes a multi-ring fused ring system, and R D and X 5 R on B They are joined together to form 5 to 10-membered rings.

[0161] In some implementation schemes, R D It is a multi-ring fused ring system containing exactly two rings.

[0162] In some implementation schemes, R D It is a multi-ring fused ring system containing at least two rings.

[0163] In some implementation schemes, R D It is a multi-ring fused ring system containing exactly 3 rings.

[0164] In some implementation schemes, R D Selected from naphthalene, quinoline, isoquinoline, quinazoline, quinoxaline, benzofuran, aza-benzofuran, benzoxazole, aza-benzoxazole, benzothiophene, aza-benzothiophene, benzothiazole, aza-benzothiazole, benzoselenophenol, aza-benzoselenophene, indene, aza-indene, indole, aza-indole, benzimidazole, aza-benzimidazole, carbazole, aza-carbazole, naphthemidazole (benzobenzimidazole), dibenzofuran, aza-dibenzofuran, dibenzothiazole, aza-dibenzothiazole, phthalazine, phenanthrene, aza-phenanthrene, anthracene, aza-anthracene, phenanthridine, fluorene, and aza-fluorene.

[0165] In some implementation schemes, R D and X 5 R on B They are joined together to form a 5-membered ring.

[0166] In some implementation schemes, R D and X 5 R on B They are joined together to form a 6-membered ring.

[0167] In some implementation schemes, R B Selected from alkyl, heteroalkyl, alkenyl and heteroalkenyl groups.

[0168] In some implementation schemes, R B It is a methyl group.

[0169] In some embodiments, structural part B is selected from benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole, and triazole.

[0170] In some implementations, structural part B is benzene.

[0171] In some implementation schemes, X 4 It's C.

[0172] In some implementation schemes, X 5 It's C.

[0173] In some implementation schemes, R α R β R A R B R C RC’ and R D Each of them is independently hydrogen or a substituent selected from the following: deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silalkyl, germanalkyl, boroalkyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thio, and combinations thereof.

[0174] In some implementations, the metal M is selected from Ir, Rh, Re, Ru, Os, Pt, Pd, Ag, Au, and Cu.

[0175] In some implementations, M is selected from Ir, Pd, and Pt.

[0176] In some implementations, M is Ir.

[0177] In some implementations, M is Pt.

[0178] In some implementations, M is Pd.

[0179] In some implementation schemes, Z 1 It is BR C In some implementation schemes, Z 1 It is Gar. C In some implementation schemes, Z 1 It is SiR C R C’ In some implementation schemes, Z 1 It is GeR C R C’ .

[0180] In some implementation schemes, Z 1 It is BR C And R C It contains at least one aromatic ring.

[0181] In some implementation schemes, Z 1 It is BR C And R C It contains at least one 6-membered aromatic ring.

[0182] In some implementation schemes, Z 1 It is BR C And R C It contains at least one 6-membered carbon ring aromatic ring.

[0183] In some implementation schemes, Z 1 It is BR C And R C It contains at least two aromatic rings.

[0184] In some implementation schemes, Z 1 It is BR CAnd R C It contains at least two 6-membered aromatic rings.

[0185] In some implementation schemes, Z 1 It is BR C And R C It contains at least two six-membered carbon-ring aromatic rings. In some embodiments, Z 1 It is BR C And R C Contains an alkyl-substituted aromatic ring. In some embodiments, Z 1 It is BR C And R C It contains 2,6-dialkyl aromatic rings.

[0186] In some implementation schemes, Z 1 It is C=O.

[0187] In some implementation schemes, Z 1 It is C=S.

[0188] In some implementation schemes, Z 1 It is C=Se.

[0189] In some implementation schemes, X 1 -X 5 At least one of them is N.

[0190] In some implementation schemes, X 1 -X 5 One of them is N.

[0191] In some implementation schemes, X 1 -X 5 At least two of them are N.

[0192] In some implementation schemes, X 1 It is N.

[0193] In some implementation schemes, X 1 and X 3 It is N.

[0194] In some implementation schemes, X 2 It is N.

[0195] In some implementation schemes, X 2 It's C.

[0196] In some implementation schemes, X 3 It is N and X 4 It's C.

[0197] In some implementation schemes, X 3 It is C and X 4 It is N.

[0198] In some implementation schemes, X 3 It's C.

[0199] In some implementation schemes, K 1 and K 2 One of them is selected from O, S, N(R) α ), P(R α ), B(R) α ), C(R α (R) β ), and Si(R) α (R) β ).

[0200] In some implementation schemes, K 1 and K 2 Both are direct keys.

[0201] In some implementation schemes, Z 2 It is NR D .

[0202] In some implementation schemes, Z 2 It is NR D And R D and X 5 R on B A ring is formed.

[0203] In some implementation schemes, Z 2 It is NR D And R D and X 5 R on B A 6-membered ring is formed.

[0204] In some implementation schemes, Z 2 It is O.

[0205] In some implementation schemes, Z 2 It is S.

[0206] In some implementation schemes, Z 1 It is BR C And Z 2 It is NR D .

[0207] In some implementation schemes, Z 1 It is BR C And Z 2 It is O.

[0208] In some implementation schemes, Z 1 It is C=O and Z 2 It is NR D .

[0209] In some implementation schemes, Z 1 It is C=O and Z 2 It is O.

[0210] In some implementations, all R A They're all hydrogen.

[0211] In some implementations, all R B They're all hydrogen.

[0212] In some embodiments, structural moiety A is selected from the following list of cyclic moieties: benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole, triazole, naphthalene, quinoline, isoquinoline, quinazoline, benzofuran, aza-benzofuran, phenanthro[3,2-b]benzofuran, benzoxazole, aza-benzoxazole, benzothiophene, aza-benzothiophene, benzothiazole, aza-benzene Benzyl thiazole, benzo[selenophenol], aza-benzo[selenophenol], indene, aza-indene, indole, aza-indole, benzimidazole, aza-benzimidazole, carbazole, aza-carbazole, naphthemidazole (benzo[benzimidazole]), dibenzofuran, aza-dibenzofuran, dibenzothiophene, aza-dibenzothiophene, quinoxaline, phthalazine, phenanthrene, aza-phenanthrene, anthracene, aza-anthracene, phenanthridine, fluorene, and aza-fluorene.

[0213] In some embodiments, the nitrile variant includes an N atom on the benzo[a] ring. In some embodiments, the nitrile variant includes an N atom on the benzo[a] ring, and the N atom is coupled to the metal M.

[0214] In some implementations, structural part A is a single-ring ring.

[0215] In some embodiments, structural part A is selected from benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole, and triazole.

[0216] In some implementations, structural part A is benzene, pyrimidine, or pyridine.

[0217] In some implementations, structural part A is pyridine.

[0218] In some implementations, structural part A is a pyrimidine.

[0219] In some implementations, structural part A is a multi-ring fused ring system.

[0220] In some embodiments, structural part A is selected from naphthalene, quinoline, isoquinoline, quinazoline, quinoxaline, benzofuran, aza-benzofuran, benzoxazole, aza-benzoxazole, benzothiophene, aza-benzothiophene, benzothiazole, aza-benzothiazole, benzoselenophenol, aza-benzoselenophene, indene, aza-indene, indole, aza-indole, benzimidazole, aza-benzimidazole, carbazole, aza-carbazole, naphthemidazole (benzobenzimidazole), dibenzofuran, aza-dibenzofuran, dibenzothiazole, aza-dibenzothiazole, phthalazine, phenanthrene, aza-phenanthrene, anthracene, aza-anthracene, phenanthridine, fluorene, and aza-fluorene.

[0221] In some embodiments, structural part A is naphthalene, quinoline, benzofuran, aza-benzofuran, benzothiophene, aza-benzothiophene, benzimidazole, aza-benzothiophene, carbazole, aza-carbazole, naphthemidazole (benzobenzimidazole), dibenzofuran, aza-dibenzofuran, dibenzothiophene, or aza-dibenzothiophene.

[0222] In some embodiments, structural moiety B is selected from the following list of cyclic moieties: benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole, triazole, naphthalene, quinoline, isoquinoline, quinazoline, benzofuran, aza-benzofuran, phenanthro[3,2-b]benzofuran, benzoxazole, aza-benzoxazole, benzothiophene, aza-benzothiophene, benzothiazole, aza-benzene Benzylthiazole, benzo[selenophenol], aza-benzo[selenophenol], indene, aza-indene, indole, aza-indole, benzimidazole, aza-benzimidazole, carbazole, aza-carbazole, naphthemidazole (benzobenzimidazole), dibenzofuran, aza-dibenzofuran, dibenzothiophene, aza-dibenzothiophene, quinoxaline, phthalazine, phenanthrene, aza-phenanthrene, anthracene, aza-anthracene, phenanthridine, fluorene, and aza-fluorene.

[0223] In some embodiments, the nitrile variant includes an N atom on the benzo[a] ring. In some embodiments, the nitrile variant includes an N atom on the benzo[a] ring, and the N atom is coupled to the metal M.

[0224] In some implementations, structural part B is a single-ring ring.

[0225] In some embodiments, structural part B is selected from benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole, and triazole.

[0226] In some implementations, structural part B is benzene, pyrimidine, or pyridine.

[0227] In some implementations, structural part B is a pyrimidine.

[0228] In some implementations, structural part B is pyridine.

[0229] In some implementations, structural part B is a multi-ring fused ring system.

[0230] In some embodiments, structural part B is selected from naphthalene, quinoline, isoquinoline, quinazoline, quinoxaline, benzofuran, aza-benzofuran, benzoxazole, aza-benzoxazole, benzothiophene, aza-benzothiophene, benzothiazole, aza-benzothiazole, benzoselenophenol, aza-benzoselenophene, indene, aza-indene, indole, aza-indole, benzimidazole, aza-benzimidazole, carbazole, aza-carbazole, naphthemidazole (benzobenzimidazole), dibenzofuran, aza-dibenzofuran, dibenzothiazole, aza-dibenzothiazole, phthalazine, phenanthrene, aza-phenanthrene, anthracene, aza-anthracene, phenanthridine, fluorene, and aza-fluorene.

[0231] In some embodiments, structural part B is naphthalene, quinoline, benzofuran, aza-benzofuran, benzothiophene, aza-benzothiophene, benzimidazole, aza-benzothiophene, carbazole, aza-carbazole, naphthemidazole (benzobenzimidazole), dibenzofuran, aza-dibenzofuran, dibenzothiophene, or aza-dibenzothiophene.

[0232] In some implementations, ligand L A Select the group consisting of the following structure (LIST 1):

[0233] , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , and ;

[0234] Where X 6 To X 19 Each can be independently represented as C or N;

[0235] Z 3 and Z 4 Each is independently selected from O, S, and NR. a BR a C(R) a (R) b ) and Si(R a (R) b );

[0236] Z 5 It is B or N; and

[0237] Each R', R a R b R AA R BB R CC R CC’ and R DD Independently hydrogen or a substituent selected from the following: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silalkyl, germanalkyl, boronalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphinyl, boronyl, selenyl, and combinations thereof.

[0238] In some implementations, the ligand L A It is a structure selected from LIST 1, with at least one R a R b R AA R BB R CC R CC’ R DD Alternatively, R' may be selected from generic substituents as defined herein. In some embodiments, at least one R AA Selected from generic substituents as defined herein. In some embodiments, at least one R BB Selected from generic substituents as defined herein. In some embodiments, at least one R CC Selected from generic substituents as defined herein. In some embodiments, at least one R CC’ Selected from generic substituents as defined herein. In some embodiments, at least one R DDThe substituent is selected from universal substituents as defined herein. In some embodiments, at least one R' is selected from universal substituents as defined herein. In some embodiments, at least one R... a Or R b Selected from universal substituents as defined in this article.

[0239] In ligand L A In some implementation schemes selected from LIST 1, at least one R a R b R AA R BB R CC R CC’ R DD Alternatively, R' may be selected from preferred general substituents as defined herein. In some embodiments, at least one R AA Selected from preferred general substituents as defined herein. In some embodiments, at least one R BB Selected from preferred general substituents as defined herein. In some embodiments, at least one R CC Selected from preferred general substituents as defined herein. In some embodiments, at least one R CC’ Selected from preferred general substituents as defined herein. In some embodiments, at least one R DD The substituents are selected from preferred general substituents as defined herein. In some embodiments, at least one R' is selected from preferred general substituents as defined herein. In some embodiments, at least one R... a Or R b Selected from preferred general substituents as defined herein.

[0240] In ligand L A In some implementation schemes selected from LIST 1, at least one R a R b R AA R BB R CC R CC’ R DD Or R' is partially or completely deuterated. In some embodiments, at least one R AA It is partially or completely deuterated. In some embodiments, at least one R BB It is partially or completely deuterated. In some embodiments, at least one R CC It is partially or completely deuterated. In some embodiments, at least one R CC’ It is partially or completely deuterated. In some embodiments, at least one R DD It is partially or completely deuterated. In some embodiments, at least one R' is partially or completely deuterated. In some embodiments, at least one Ra Or R b It is partially or completely deuterated.

[0241] In ligand L A In some implementation schemes selected from LIST 1, at least one R AA It is or contains an electron-withdrawing group from an EWG1 LIST as defined herein. In some embodiments, at least one R AA It is or contains an electron-withdrawing group from EWG2 LIST as defined herein. In some embodiments, at least one R AA It is or contains an electron-withdrawing group from EWG3 LIST as defined herein. In some embodiments, at least one R AA It is or contains an electron-withdrawing group from EWG4 LIST as defined herein. In some embodiments, at least one R AA It is or contains electron-withdrawing groups from Pi-EWG LIST as defined herein.

[0242] In ligand L A In some implementation schemes selected from LIST 1, at least one R BB It is or contains an electron-withdrawing group from an EWG1 LIST as defined herein. In some embodiments, at least one R BB It is or contains an electron-withdrawing group from EWG2 LIST as defined herein. In some embodiments, at least one R BB It is or contains an electron-withdrawing group from EWG3 LIST as defined herein. In some embodiments, at least one R BB It is or contains an electron-withdrawing group from EWG4 LIST as defined herein. In some embodiments, at least one R BB It is or contains electron-withdrawing groups from Pi-EWG LIST as defined herein.

[0243] In ligand L A In some implementation schemes selected from LIST 1, at least one R CC It is or contains an electron-withdrawing group from an EWG1 LIST as defined herein. In some embodiments, at least one R CC It is or contains an electron-withdrawing group from EWG2 LIST as defined herein. In some embodiments, at least one R CC It is or contains an electron-withdrawing group from EWG3 LIST as defined herein. In some embodiments, at least one R CC It is or contains an electron-withdrawing group from EWG4 LIST as defined herein. In some embodiments, at least one R CCIt is or contains electron-withdrawing groups from Pi-EWG LIST as defined herein.

[0244] In ligand L A In some implementation schemes selected from LIST 1, at least one R CC’ It is or contains an electron-withdrawing group from an EWG1 LIST as defined herein. In some embodiments, at least one R CC’ It is or contains an electron-withdrawing group from EWG2 LIST as defined herein. In some embodiments, at least one R CC’ It is or contains an electron-withdrawing group from EWG3 LIST as defined herein. In some embodiments, at least one R CC’ It is or contains an electron-withdrawing group from EWG4 LIST as defined herein. In some embodiments, at least one R CC’ It is or contains electron-withdrawing groups from Pi-EWG LIST as defined herein.

[0245] In ligand L A In some implementation schemes selected from LIST 1, at least one R DD It is or contains an electron-withdrawing group from an EWG1 LIST as defined herein. In some embodiments, at least one R DD It is or contains an electron-withdrawing group from EWG2 LIST as defined herein. In some embodiments, at least one R DD It is or contains an electron-withdrawing group from EWG3 LIST as defined herein. In some embodiments, at least one R DD It is or contains an electron-withdrawing group from EWG4 LIST as defined herein. In some embodiments, at least one R DD It is or contains electron-withdrawing groups from Pi-EWG LIST as defined herein.

[0246] In ligand L A In some embodiments selected from LIST 1, at least one R' is or contains an electron-withdrawing group from an EWG1 LIST as defined herein. In some embodiments, at least one R' is or contains an electron-withdrawing group from an EWG2 LIST as defined herein. In some embodiments, at least one R' is or contains an electron-withdrawing group from an EWG3 LIST as defined herein. In some embodiments, at least one R' is or contains an electron-withdrawing group from an EWG4 LIST as defined herein. In some embodiments, at least one R' is or contains an electron-withdrawing group from a Pi-EWG LIST as defined herein.

[0247] In ligand LA In some implementation schemes selected from LIST 1, at least one R a Or R b It is or contains an electron-withdrawing group from an EWG1 LIST as defined herein. In some embodiments, at least one R a Or R b It is or contains an electron-withdrawing group from EWG2 LIST as defined herein. In some embodiments, at least one R a Or R b It is or contains an electron-withdrawing group from EWG3 LIST as defined herein. In some embodiments, at least one R a Or R b It is or contains an electron-withdrawing group from EWG4 LIST as defined herein. In some embodiments, at least one R a Or R b It is or contains electron-withdrawing groups from Pi-EWG LIST as defined herein.

[0248] In some implementations, ligand L A Select the group consisting of the following structure (LIST 2):

[0249] , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , and .

[0250] In ligand L A These are some implementations of the structure selected from LIST 2, at least one R a R b R AA R BB R CC R CC’ R DD Alternatively, R' may be selected from generic substituents as defined herein. In some embodiments, at least one R AASelected from generic substituents as defined herein. In some embodiments, at least one R BB Selected from generic substituents as defined herein. In some embodiments, at least one R CC Selected from generic substituents as defined herein. In some embodiments, at least one R CC’ Selected from generic substituents as defined herein. In some embodiments, at least one R DD The substituent is selected from universal substituents as defined herein. In some embodiments, at least one R' is selected from universal substituents as defined herein. In some embodiments, at least one R... a Or R b Selected from universal substituents as defined in this article.

[0251] In ligand L A Selected from some implementations of LIST 2, at least one R a R b R AA R BB R CC R CC’ R DD Alternatively, R' may be selected from preferred general substituents as defined herein. In some embodiments, at least one R AA Selected from preferred general substituents as defined herein. In some embodiments, at least one R BB Selected from preferred general substituents as defined herein. In some embodiments, at least one R CC Selected from preferred general substituents as defined herein. In some embodiments, at least one R CC’ Selected from preferred general substituents as defined herein. In some embodiments, at least one R DD The substituents are selected from preferred general substituents as defined herein. In some embodiments, at least one R' is selected from preferred general substituents as defined herein. In some embodiments, at least one R... a Or R b Selected from preferred general substituents as defined herein.

[0252] In ligand L A Selected from some implementations of LIST 2, at least one R a R b R AA R BB R CC R CC’ R DD Or R' is partially or completely deuterated. In some embodiments, at least one R AA It is partially or completely deuterated. In some embodiments, at least one RBB It is partially or completely deuterated. In some embodiments, at least one R CC It is partially or completely deuterated. In some embodiments, at least one R CC’ It is partially or completely deuterated. In some embodiments, at least one R DD It is partially or completely deuterated. In some embodiments, at least one R' is partially or completely deuterated. In some embodiments, at least one R a Or R b It is partially or completely deuterated.

[0253] In ligand L A Selected from some implementations of LIST 2, at least one R AA It is or contains an electron-withdrawing group from an EWG1 LIST as defined herein. In some embodiments, at least one R AA It is or contains an electron-withdrawing group from EWG2 LIST as defined herein. In some embodiments, at least one R AA It is or contains an electron-withdrawing group from EWG3 LIST as defined herein. In some embodiments, at least one R AA It is or contains an electron-withdrawing group from EWG4 LIST as defined herein. In some embodiments, at least one R AA It is or contains electron-withdrawing groups from Pi-EWG LIST as defined herein.

[0254] In ligand L A Selected from some implementations of LIST 2, at least one R BB It is or contains an electron-withdrawing group from an EWG1 LIST as defined herein. In some embodiments, at least one R BB It is or contains an electron-withdrawing group from EWG2 LIST as defined herein. In some embodiments, at least one R BB It is or contains an electron-withdrawing group from EWG3 LIST as defined herein. In some embodiments, at least one R BB It is or contains an electron-withdrawing group from EWG4 LIST as defined herein. In some embodiments, at least one R BB It is or contains electron-withdrawing groups from Pi-EWG LIST as defined herein.

[0255] In ligand L A Selected from some implementations of LIST 2, at least one R CC It is or contains an electron-withdrawing group from an EWG1 LIST as defined herein. In some embodiments, at least one R CCIt is or contains an electron-withdrawing group from EWG2 LIST as defined herein. In some embodiments, at least one R CC It is or contains an electron-withdrawing group from EWG3 LIST as defined herein. In some embodiments, at least one R CC It is or contains an electron-withdrawing group from EWG4 LIST as defined herein. In some embodiments, at least one R CC It is or contains electron-withdrawing groups from Pi-EWG LIST as defined herein.

[0256] In ligand L A Selected from some implementations of LIST 2, at least one R CC’ It is or contains an electron-withdrawing group from an EWG1 LIST as defined herein. In some embodiments, at least one R CC’ It is or contains an electron-withdrawing group from EWG2 LIST as defined herein. In some embodiments, at least one R CC’ It is or contains an electron-withdrawing group from EWG3 LIST as defined herein. In some embodiments, at least one R CC’ It is or contains an electron-withdrawing group from EWG4 LIST as defined herein. In some embodiments, at least one R CC’ It is or contains electron-withdrawing groups from Pi-EWG LIST as defined herein.

[0257] In ligand L A Selected from some implementations of LIST 2, at least one R DD It is or contains an electron-withdrawing group from an EWG1 LIST as defined herein. In some embodiments, at least one R DD It is or contains an electron-withdrawing group from EWG2 LIST as defined herein. In some embodiments, at least one R DD It is or contains an electron-withdrawing group from EWG3 LIST as defined herein. In some embodiments, at least one R DD It is or contains an electron-withdrawing group from EWG4 LIST as defined herein. In some embodiments, at least one R DD It is or contains electron-withdrawing groups from Pi-EWG LIST as defined herein.

[0258] In ligand L AIn some embodiments selected from LIST 2, at least one R' is or contains an electron-withdrawing group from an EWG1 LIST as defined herein. In some embodiments, at least one R' is or contains an electron-withdrawing group from an EWG2 LIST as defined herein. In some embodiments, at least one R' is or contains an electron-withdrawing group from an EWG3 LIST as defined herein. In some embodiments, at least one R' is or contains an electron-withdrawing group from an EWG4 LIST as defined herein. In some embodiments, at least one R' is or contains an electron-withdrawing group from a Pi-EWG LIST as defined herein.

[0259] In ligand L A Selected from some implementations of LIST 2, at least one R a Or R b It is or contains an electron-withdrawing group from an EWG1 LIST as defined herein. In some embodiments, at least one R a Or R b It is or contains an electron-withdrawing group from EWG2 LIST as defined herein. In some embodiments, at least one R a Or R b It is or contains an electron-withdrawing group from EWG3 LIST as defined herein. In some embodiments, at least one R a Or R b It is or contains an electron-withdrawing group from EWG4 LIST as defined herein. In some embodiments, at least one R a Or R b It is or contains electron-withdrawing groups from Pi-EWG LIST as defined herein.

[0260] In some embodiments, the ligand L A Selected from L A W1-(R i (R) j (R) k (R) l ) and L A W2-(R j (R) k (R) l ), where W1 is an integer from 1 to 263, 265, 267 to 280, 282, 284 to 489, W2 is 264, 266, 281, and 283, and each i, j, k, and l is an independent integer from 1 to 263, and each R i R j R k and R l Independently selected from V1 to V263, and each LA W1-(R i (R) j (R) k (R) l ) and L A W2-(R j (R) k (R) l Defined in the following table (LIST 3):

[0261]

[0262]

[0263]

[0264]

[0265]

[0266]

[0267]

[0268]

[0269]

[0270]

[0271]

[0272]

[0273]

[0274]

[0275]

[0276]

[0277]

[0278]

[0279]

[0280]

[0281]

[0282]

[0283]

[0284]

[0285]

[0286]

[0287]

[0288]

[0289]

[0290]

[0291]

[0292]

[0293]

[0294]

[0295]

[0296]

[0297]

[0298]

[0299]

[0300]

[0301]

[0302]

[0303]

[0304]

[0305]

[0306]

[0307] Among them, V1 to V263 have the following LIST A structure:

[0308] , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , ,and .

[0309] In some embodiments, the compound has the formula M(L) A ) p (L B ) q (L C ) r L B and L C Each is a bidentate ligand; and p is 1, 2 or 3; q is 0, 1 or 2; r is 0, 1 or 2; and p+q+r is the oxidation state of metal M.

[0310] In some embodiments, the compound has a composition selected from Ir(L) A )3, Ir(L A (L) B )2、Ir(L A )2(L B ), Ir(L A )2(L C ), and Ir(L A (L) B (L) C The formula is: ) and where L A L B and L C They are different from each other.

[0311] In some implementations, L B It is a substituted or unsubstituted phenylpyridine, L C It is a substituted or unsubstituted acetylacetone compound.

[0312] In some embodiments, the compound has the formula Pt(L) A (L) B ); and L A and L B They can be the same or different.

[0313] In some implementations, L A and L B They connect to form tetradentate ligands.

[0314] In some implementations, L B and L C Each group is independently selected from the following structures (LIST 4):

[0315] , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , and ;

[0316] in:

[0317] T is selected from B, Al, Ga, and In;

[0318] Where K 1’ Is it a direct key or selected from NR? e PR e , O, S and Se;

[0319] Y 1 To Y 13 Each of them is independently selected from carbon and nitrogen;

[0320] Y' is selected from BR e NR e PR e ,O,S,Se,C=O,C=S,C=Se,S=O,SO2,P(O)R e C=NR e C=CR e R f CR e R f SiR e R f and GeR e R f ;

[0321] R e and R f They can be fused or joined to form rings;

[0322] Each R a R b R c and R d Independently represents zero substitution, single substitution, or the maximum permissible number of substitutions for its associated loops;

[0323] R a1 R b1 R c1 R d1 R a R b R c R d R e and R fEach of these groups is independently hydrogen or a substituent selected from the following: deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germanyl, boranyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphinyl, selenyl, and combinations thereof; general substituents as defined herein; and

[0324] Any two adjacent R a R b R c R d R e and R f They can fused or joined to form rings or form multidentate ligands.

[0325] In some implementations, L B and L C Each group is independently selected from the following structures (LIST 5):

[0326] , , , ,

[0327] , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , ,

[0328] , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , and ;

[0329] Where R a '、R b '、R c '、R d 'and R e Each can be used independently to indicate zero substitution, single substitution, or up to the maximum permissible substitution in relation to its associated loop;

[0330] Where R a '、R b '、R c '、R d 'and R e Each of the following substituents is independently hydrogen or selected from: deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germanyl, boranyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphinyl, selenyl, and combinations thereof; and

[0331] Where R a '、R b '、R c '、R d 'and R e Two adjacent substituents in ' can fuse or join to form a ring or a polydentate ligand.

[0332] In some implementations, L B Include The structure, where the variants are the same as those previously defined. In some implementations, Y 1a To Y 4a Each of them is independently carbon. In some implementations, Y 1a To Y 4a At least one of them is N. In some implementations, Y 1a To Y 4a One of them is N. In some implementations, Y 1a It is N. In some implementations, Y 2a It is N. In some implementations, Y 3a It is N. In some implementations, Y 4a It is N.

[0333] In some implementation schemes, R aAt least one of them is a tertiary alkyl, silyl, or germanyl group. In some embodiments, R a At least one of them is a tertiary alkyl group.

[0334] In some implementation schemes, Y 1a It is carbon and is connected to R a1 In some such implementations, R a1 It can be selected from generic substituents as defined herein. In some such implementations, R a1 It can be selected from preferred general substituents as defined herein. In some such embodiments, R a1 It is a tertiary alkyl, silyl, or germanyl group. In some such embodiments, R a1 It is a tertiary alkyl group. In some embodiments, Y 2a It is carbon and is connected to R a2 In some such implementations, R a2 It can be selected from generic substituents as defined herein. In some such implementations, R a2 It can be selected from preferred general substituents as defined herein. In some such embodiments, R a2 It is a tertiary alkyl, silyl, or germanyl group. In some such embodiments, R a2 It is a tertiary alkyl group. In some embodiments, Y 3a It is carbon and is connected to R a3 In some such implementations, R a3 It can be selected from generic substituents as defined herein. In some such implementations, R a3 It can be selected from preferred general substituents as defined herein. In some such embodiments, R a3 It is a tertiary alkyl, silyl, or germanyl group. In some such embodiments, R a3 It is a tertiary alkyl group. In some embodiments, Y 4a It is carbon and is connected to R a4 In some such implementations, R a4 It can be selected from generic substituents as defined herein. In some such implementations, R a4 It can be selected from preferred general substituents as defined herein. In some such embodiments, R a4 It is a tertiary alkyl, silyl, or germanyl group. In some such embodiments, R a4 It is a tertiary alkyl group.

[0335] In some implementation schemes, X 3a It is C, and R is connected to it. C It is a tertiary alkyl, silyl, or germanyl group. In some embodiments, X 2aIt is C, and R is connected to it. C It is a tertiary alkyl, silyl, or germanyl group.

[0336] In some implementation schemes, Y 1a To Y 3a It is C, Y 4a It is N, and connected to Y. 3a R a3 It is a tertiary alkyl, silyl, or germanyl group. In some embodiments, Y 1a To Y 3a It is C, Y 4a It is N, and connected to Y. 2a R a2 It is a tertiary alkyl, silyl, or germanyl group.

[0337] In some implementation schemes, R b At least one of them is a tertiary alkyl, silyl, or germanyl group. In some embodiments, R b At least one of them is tert-butyl. In some embodiments, at least one pair of R a A pair of R b Or an R a And an R b Joining or fused into rings.

[0338] In some implementation schemes, R b1 It is attached to C1 (carbon atom). In some such implementations, R b1 It can be selected from generic substituents as defined herein. In some such implementations, R b1 It can be selected from preferred general substituents as defined herein. In some such embodiments, R b1 It is a tertiary alkyl, silyl, or germanyl group. In some such embodiments, R b1 It is a tertiary alkyl group. In some embodiments, the tertiary alkyl group is a tertiary butyl group. In some embodiments, R... b2 It is attached to C2 (carbon atom). In some such implementations, R b2 It can be selected from generic substituents as defined herein. In some such implementations, R b2 It can be selected from preferred general substituents as defined herein. In some such embodiments, R b2 It is a tertiary alkyl, silyl, or germanyl group. In some such embodiments, R b2 It is a tertiary alkyl group. In some embodiments, the tertiary alkyl group is a tertiary butyl group. In some embodiments, R... b3 It is attached to C3 (carbon atom). In some such implementations, R b3 It can be selected from generic substituents as defined herein. In some such implementations, Rb3 It can be selected from preferred general substituents as defined herein. In some such embodiments, R b3 It is a tertiary alkyl, silyl, or germanyl group. In some such embodiments, R b3 It is a tertiary alkyl group. In some embodiments, the tertiary alkyl group is a tertiary butyl group. In some embodiments, R... b4 It is attached to C4 (carbon atom). In some such implementations, R b4 It can be selected from generic substituents as defined herein. In some such implementations, R b4 It can be selected from preferred general substituents as defined herein. In some such embodiments, R b4 It is a tertiary alkyl, silyl, or germanyl group. In some such embodiments, R b4 It is a tertiary alkyl group. In some embodiments, the tertiary alkyl group is a tertiary butyl group.

[0339] In some embodiments, the compound has the formula Ir(L A 3. Formula Ir(L) A (L) Bk )2. Equation Ir(L A )2(L Bk ), formula Ir(L A )2(L Cj-I ) or formula Ir(L A )2(L Cj-II ),

[0340] Where L A It is based on any one of claims 1-86;

[0341] Where k is an integer from 1 to 544, and each L Bk The structure is defined as follows (LIST 6):

[0342] , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , and ;

[0343] Each L Cj-I With a based The structure; and

[0344] Each L Cj-II With a based The structure, where for L Cj-I and L Cj-II Each L in Cj R 201 and R 202 Each is defined independently in Table A below as follows:

[0345]

[0346]

[0347]

[0348]

[0349]

[0350]

[0351]

[0352]

[0353]

[0354]

[0355]

[0356]

[0357] Where R D1 To R D246 It has the following structure as defined in LIST 8:

[0358] , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , ., , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , ,, , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , and .

[0359] In some embodiments, the compound is selected from the group consisting only of the following compounds, whose L Bk Corresponding to one of the following: L B1 , L B30 , L B31 , L B109 , L B110 , L B112 , L B113 , L B114 , L B125 , L B127 ,L B138 , L B140 , L B149 , L B150 , L B170 , L B171 , L B172 , L B174, L B208 , L B241 , L B312 , L B315 , L B356 ,L B367 , L B371 , L B382 , L B439 , L B440 , L B455 , L B456 , L B457 , L B458 , L B461 , L B462 , L B463 , L B469 , and L B476 .

[0360] In some embodiments, the compound is selected from the group consisting only of the following compounds, whose L Bk Corresponds to one of the following: L B1 , L B30 , L B31 , L B125 , L B138 , L B171 , L B172 , L B356 , L B357 , L B367 , L B371 ,L B382 , L B455 , and L B456 .

[0361] In some embodiments, the compound is selected from the group consisting only of compounds having L Cj-I or L Cj-II ligand, the L Cj-I or L Cj-II The corresponding R of the ligand 201 and R 202 Defined as one of the following structures: R D1 ,R D3 , R D4 , R D5 , R D9 , R D10 , R D17 , R D18 , R D20 , R D22 , R D37 , R D40 , R D41 , R D42, R D43 , R D48 , R D49 ,R D50 , R D54 , R D55 , R D58 , R D59 , R D78 , R D79 , R D81 , R D87 , R D88 , R D89 , R D93 , R D116 , R D117 , R D118 ,R D119 , R D120 , R D133 , R D134 , R D135 , R D136 , R D143 , R D144 , R D145 , R D146 , R D147 , R D149 , R D151 ,R D154 , R D155 , R D161 , R D175 R D190 , R D193 , R D200 , R D201 , R D206 , R D210 , R D214 , R D215 , R D216 , R D218 ,R D219 , R D220 , R D227 , R D237 , R D241 , R D242 , R D245 , and R D246 .

[0362] In some embodiments, the compound is selected from the group consisting only of compounds having L Cj-I or L Cj-II ligand, the L Cj-I or L Cj-II The corresponding R of the ligand 201 and R202 Defined as selected from one of the following structures: R D1 ,R D3 , R D4 , R D5 , R D9 , R D10 , R D17 , R D22 , R D43 , R D50 , R D78 , R D116 , R D118 , R D133 , R D134 , R D135 ,R D136 , R D143 , R D144 , R D145 , R D146 , R D149 , R D151 , R D154 , R D155 R D190 , R D193 , R D200 , R D201 , R D206 ,R D210 , R D214 , R D215 , R D216 , R D218 , R D219 , R D220 , R D227 , R D237 , R D241 , R D242 , R D245 , and R D246 .

[0363] In some embodiments, the compound is selected from the group consisting only of compounds having L Cj-I The ligand is one of the following structures defined in LIST 7 below:

[0364] , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , and .

[0365] In some embodiments, the compound has a composition selected from Ir(L) A 3. Ir(L) A )2(L B ), Ir(L A (L) B )2、Ir(L A )2(L C ) and Ir(L A (L) B (L) C The chemical formula of ). In some implementations, L A The structure is selected from LIST 1, LIST 2 and LIST 3, L B Selected from LIST 4, LIST 5 and LIST 6 (L Bk The structure of ) and L C Selected from L as defined in LIST 7 Cj-I and L Cj-II The structure.

[0366] In some implementations, L A The structure is selected from LIST 1, and L B Selected from L Bk The structure. In some implementations, L A The structure is selected from LIST 2, and L B Selected from L Bk The structure. In some implementations, L A Selected from LIST 3 as defined in this article, and LB Selected from L Bk The structure is where k is an integer from 1 to 544. In some implementations, L A Selected from LIST 1 as defined in this paper, and L C Selected from L Cj-I and L Cj-II The structure is , where j is an integer from 1 to 1416.

[0367] In some embodiments, the compound may have the formula Ir(L) consisting of the following compounds. A W1-(R i (R) j (R) k (R) l ))3:Ir(L A 1-(V1)(V1)(V1)(V1))3 to Ir(L A 263-(V263)(V263)(V263)(V263))3,Ir(L A 265-(V1)(V1)(V1)(V1))3 to Ir(L A 265-(V263)(V263)(V263)(V263))3, Ir(L A 267-(V1)(V1)(V1)(V1))3 to Ir(L A 280-(V263)(V263)(V263)(V263))3, Ir(L A 282-(V1)(V1)(V1)(V1))3 to Ir(L A 282-(V263)(V263)(V263)(V263))3, and Ir(L A 284-(V1)(V1)(V1)(V1))3 to Ir(L A 489-(V263)(V263)(V263)(V263))3, Ir(L) is composed of the following compounds. A W1-(R i (R) j (R) k (R) l ))(L Bk )2:Ir(L A 1-(V1)(V1)(V1)(V1))(L B1 )2 to Ir(L A 263-(V263)(V263)(V263)(V263))(L B544 )2, Ir(L A265-(V1)(V1)(V1)(V1))(L B1 )2 to Ir(L A 265-(V263)(V263)(V263)(V263))(L B544 )2, Ir(L A 267-(V1)(V1)(V1)(V1))(L B1 )2 to Ir(L A 280-(V263)(V263)(V263)(V263))(L B544 )2, Ir(L A 282-(V1)(V1)(V1)(V1))(L B1 )2 to Ir(L A 282-(V263)(V263)(V263)(V263))(L B544 )2, and Ir(L A 284-(V1)(V1)(V1)(V1))(L B1 )2 to Ir(L A 489-(V263)(V263)(V263)(V263))(L B544 )2, Ir(L) composed of the following compounds A W1-(R i (R) j (R) k (R) l ))2(L Bk ):Ir(L A 1-(V1)(V1)(V1)(V1))2(L B1 ) to Ir(L A 263-(V263)(V263)(V263)(V263))2(L B544 ), Ir(L A 265-(V1)(V1)(V1)(V1))2(L B1 ) to Ir(L A 265-(V263)(V263)(V263)(V263))2(L B544 ), Ir(L A 267-(V1)(V1)(V1)(V1))2(L B1 ) to Ir(L A 280-(V263)(V263)(V263)(V263))2(L B544 ), Ir(L A 282-(V1)(V1)(V1)(V1))2(L B1) to Ir(L A 282-(V263)(V263)(V263)(V263))2(L B544 ), and Ir(L A 284-(V1)(V1)(V1)(V1))2(L B1 ) to Ir(L A 489-(V263)(V263)(V263)(V263))2(L B544 ), composed of the following compounds of the formula Ir(L A W1-(R i (R) j (R) k (R) l ))2(L Cj-I ):Ir(L A 1-(V1)(V1)(V1)(V1))2(L C1-I ) to Ir(L A 263-(V263)(V263)(V263)(V263))2(L C1416-I ), Ir(L A 265-(V1)(V1)(V1)(V1))2(L C1-I ) to Ir(L A 265-(V263)(V263)(V263)(V263))2(L C1416-I ), Ir(L A 267-(V1)(V1)(V1)(V1))2(L C1-I ) to Ir(L A 280-(V263)(V263)(V263)(V263))2(L C1416-I ), Ir(L A 282-(V1)(V1)(V1)(V1))2(L C1-I ) to Ir(L A 282-(V263)(V263)(V263)(V263))2(L C1416-I ), and Ir(L A 284-(V1)(V1)(V1)(V1))2(L C1-I ) to Ir(L A 489-(V263)(V263)(V263)(V263))2(L C1416-I ), composed of the following compounds of the formula Ir(L A W1-(R i (R) j (R) k (R)l ))2(L Cj-II ):Ir(L A 1-(V1)(V1)(V1)(V1))2(L C1-II ) to Ir(L A 263-(V263)(V263)(V263)(V263))2(L C1416-II ), Ir(L A 265-(R1)(R1)(R1)(R1))2(L C1-II ) to Ir(L A 265-(V263)(V263)(V263)(V263))2(L C1416-II ), Ir(L A 267-(R1)(R1)(R1)(R1))2(L C1-II ) to Ir(L A 280-(V263)(V263)(V263)(V263))2(L C1416-II ), Ir(L A 282-(R1)(R1)(R1)(R1))2(L C1-II ) to Ir(L A 282-(V263)(V263)(V263)(V263))2(L C1416-II ), and Ir(L A 284-(R1)(R1)(R1)(R1))2(L C1-II ) to Ir(L A 489-(V263)(V263)(V263)(V263))2(L C1416-II ), composed of the following compounds of the formula Ir(L A W1-(R i (R) j (R) k (R) l ))(L Bk (L) Cj-I ): Ir(L A 1-(V1)(V1)(V1)(V1))(L B1 (L) C1-I ) to Ir(L A 263-(V263)(V263)(V263)(V263))(L B544 (L) C1416-I ), Ir(L A 265-(V1)(V1)(V1)(V1))(L B1 (L) C1-I ) to Ir(LA 265-(V263)(V263)(V263)(V263))(L B544 (L) C1416-I ), Ir(L A 267-(V1)(V1)(V1)(V1))(L B1 (L) C1-I ) to Ir(L A 280-(V263)(V263)(V263)(V263))(L B544 (L) C1416-I ), Ir(L A 282-(V1)(V1)(V1)(V1))(L B1 (L) C1-I ) to Ir(L A 282-(V263)(V263)(V263)(V263))(L B544 (L) C1416-I ), and Ir(L A 284-(V1)(V1)(V1)(V1))(L B1 (L) C1-I ) to Ir(L A 489-(V263)(V263)(V263)(V263))(L B544 (L) C1416-I ), or Ir(L) composed of the following compounds A W1-(R i (R) j (R) k (R) l ))(L Bk (L) Cj-II ):Ir(L A 1-(V1)(V1)(V1)(V1))(L B1 (L) C1-II ) to Ir(L A 263-(V263)(V263)(V263)(V263))(L B544 (L) C1416-II ), Ir(L A 265-(V1)(V1)(V1)(V1))(L B1 (L) C1-II ) to Ir(L A 265-(V263)(V263)(V263)(V263))(L B544 (L) C1416-II ), Ir(L A267-(V1)(V1)(V1)(V1))(L B1 (L) C1-II ) to Ir(L A 280-(V263)(V263)(V263)(V263))(L B544 (L) C1416-II ), Ir(L A 282-(V1)(V1)(V1)(V1))(L B1 (L) C1-II ) to Ir(L A 282-(V263)(V263)(V263)(V263))(L B544 (L) C1416-II ), and Ir(L A 284-(V1)(V1)(V1)(V1))(L B1 (L) C1-II ) to Ir(L A 489-(V263)(V263)(V263)(V263))(L B544 (L) C1416-II ), where L A W1-(R i (R) j (R) k (R) l L Bk and L Cj-I and L Cj-II All are as defined in this article.

[0368] In some embodiments, the compound may have the formula Ir(L) consisting of the following compounds. A W2-R j (R) k (R) l ))3:Ir(L A 264-(V1)(V1)(V1))3 to Ir(L A 264-(V263)(V263)(V263))3, Ir(L A 266-(V1)(V1)(V1))3 to Ir(L A 266-(V263)(V263)(V263))3, Ir(L A 281-(V1)(V1)(V1))3 to Ir(L A 281-(V263)(V263)(V263))3, Ir(L A 283-(V1)(V1)(V1))3 to Ir(L A283-(V263)(V263)(V263))3, Ir(L) is composed of the following compounds. A W2-(R j (R) k (R) l ))(L Bk )2:Ir(L A 264-(V1)(V1)(V1))(L B1 )2 to Ir(L A 264-(V263)(V263)(V263))(L B544 )2, Ir(L A 266-(V1)(V1)(V1))(L B1 )2 to Ir(L A 266-(V263)(V263)(V263))(L B544 )2, Ir(L A 281-(V1)(V1)(V1))(L B1 )2 to Ir(L A 281-(V263)(V263)(V263))(L B544 )2, and Ir(L A 283-(V1)(V1)(V1))(L B1 )2 to Ir(L A 283-(V263)(V263)(V263))(L B544 )2, Ir(L) composed of the following compounds A W2-(R j (R) k (R) l ))2(L Bk ):Ir(L A 264-(V1)(V1)(V1))2(L B1 ) to Ir(L A 264-(V263)(V263)(V263))2(L B544 ), Ir(L A 266-(V1)(V1)(V1))2(L B1 ) to Ir(L A 266-(V263)(V263)(V263))2(L B544 ), Ir(L A 281-(V1)(V1)(V1))2(L B1 ) to Ir(L A 281-(V263)(V263)(V263))2(L B544), and Ir(L A 283-(V1)(V1)(V1))2(L B1 ) to Ir(L A 283-(V263)(V263)(V263))2(L B544 ), composed of the following compounds of the formula Ir(L A W2-(R j (R) k (R) l ))2(L Cj-I ): Ir(L A 264-(V1)(V1)(V1))2(L C1-I ) to Ir(L A 264-(V263)(V263)(V263))2(L C1416-I ),Ir(L A 266-(V1)(V1)(V1))2(L C1-I ) to Ir(L A 266-(V263)(V263)(V263))2(L C1416-I ), Ir(L A 281-(V1)(V1)(V1))2(L C1-I ) to Ir(L A 281-(V263)(V263)(V263))2(L C1416-I ), and Ir(L A 283-(V1)(V1)(V1))2(L C1-I ) to Ir(L A 283-(V263)(V263)(V263))2(L C1416-I ), composed of the following compounds of the formula Ir(L A W2-(R j (R) k (R) l ))2(L Cj-II ): Ir(L A 264-(V1)(V1)(V1))2(L C1-II ) to Ir(L A 264-(V263)(V263)(V263))2(L C1416-II ), Ir(L A 266-(V1)(V1)(V1))2(L C1-II ) to Ir(L A 266-(V263)(V263)(V263))2(L C1416-II ), Ir(L A281-(V1)(V1)(V1))2(L C1-II ) to Ir(L A 281-(V263)(V263)(V263))2(L C1416-II ), and Ir(L A 283-(V1)(V1)(V1))2(L C1-II ) to Ir(L A 283-(V263)(V263)(V263))2(L C1416-II ), composed of the following compounds of the formula Ir(L A W2-(R j (R) k (R) l ))(L Bk (L) Cj-I ): Ir(L A 264-(V1)(V1)(V1))(L B1 (L) C1-I ) to Ir(L A 264-(V263)(V263)(V263))(L B544 (L) C1416-I ),Ir(L A 266-(V1)(V1)(V1))(L B1 (L) C1-I ) to Ir(L A 266-(V263)(V263)(V263))(L B544 (L) C1416-I ),Ir(L A 281-(V1)(V1)(V1))(L B1 (L) C1-I ) to Ir(L A 281-(V263)(V263)(V263))(L B544 (L) C1416-I ), and Ir(L A 283-(V1)(V1)(V1))(L B1 (L) C1-I ) to Ir(L A 283-(V263)(V263)(V263))(L B544 (L) C1416-I ), or Ir(L) composed of the following compounds A W2-(R j (R) k (R) l ))(L Bk (L) Cj-II): Ir(L A 264-(V1)(V1)(V1))(L B1 (L) C1-II ) to Ir(L A 264-(V263)(V263)(V263))(L B544 (L) C1416-II ), Ir(L A 266-(V1)(V1)(V1))(L B1 (L) C1-II ) to Ir(L A 266-(V263)(V263)(V263))(L B544 (L) C1416-II ),Ir(L A 281-(V1)(V1)(V1))(L B1 (L) C1-II ) to Ir(L A 281-(V263)(V263)(V263))(L B544 (L) C1416-II ), and Ir(L A 283-(V1)(V1)(V1))(L B1 (L) C1-II ) to Ir(L A 283-(V263)(V263)(V263))(L B544 (L) C1416-II ), where L A W2-(R j (R) k (R) l L Bk and L Cj-I and L Cj-II All are as defined in this article.

[0369] In some embodiments, the compound is selected from the structures in List 9 below:

[0370] , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , ,and .

[0371] In some embodiments, the compound comprises the structure of formula II:

[0372] Formula II,

[0373] in:

[0374] M 1 It is either Pd or Pt;

[0375] X 20 Z 5 and X 21 Optionally joined or fused into structural part E;

[0376] X 22 Z 6 and X 23 Optionally joined or fused into structural part F;

[0377] Structural part E (if it exists) is optionally controlled by R E Substitution, which refers to single substitution up to the maximum permissible substitution;

[0378] The structural part F (if it exists) is optionally controlled by R. F Substitution, which refers to single substitution up to the maximum permissible substitution;

[0379] Structural parts E (if present) and F (if present) are each independently a monocyclic ring or a polycyclic fused ring system, wherein each ring of the monocyclic ring or the polycyclic fused ring system is independently a 5- to 10-membered carbon ring or a heterocyclic ring.

[0380] X 20 To X 23 Each can be independently represented as C or N; Z 5 and Z 6 Each can be independently represented as C or N;

[0381] K 1 K 2 K 3 and K 4 Each is independently selected from direct bonds, O, S, N(R) α ), P(R α ), B(R) α ), C(R α (R) β ) and Si(R α (R) β ), where at least two of them are direct bonds;

[0382] Two adjacent R A R B R E and R F They can be joined or fused together, where chemically feasible, to form a ring; and

[0383] Z 1 Z 2 Structural part A, Structural part B, R A R B R C and R D The definitions are the same as those above; among which Indicates a single or double bond; where X 20 L 1 and X 7 Between Indicates a direct key or no key; where X 23 L 3 and X 10 Between Indicates a direct key or no key; L 1 L 2 and L 3Each is independently selected from single bond, non-existent bond, BR, BRR', NR, PR, P(O)R, O, S, Se, C=O, C=S, C=Se, C=NR, C=CRR', S=O, SO2, CR, CRR', SiRR', and GeRR', among which L exists. 1 and L 3 At least one of them;

[0384] Where L 1 When it exists, L 1 Selected from direct bonds, BR, BRR′, NR, PR, P(O)R, O, S, Se, C=O, C=S, C=Se, C=NR, C=CRR', S=O, SO2, CR, CRR′, SiRR′, and GeRR′, where L 3 When it exists, L 3 Selected from direct bonds, BR, BRR′, NR, PR, P(O)R, O, S, Se, C=O, C=S, C=Se, C=NR, C=CRR', S=O, SO2, CR, CRR′, SiRR′, and GeRR′.

[0385] R, R′, R E (If it exists) and R F Each of (if present) is independently hydrogen or a substituent selected from the following: deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silalkyl, germanalkyl, boroalkyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thioyl, and combinations thereof.

[0386] And at least one of the following eleven conditions is true:

[0387] 1) Structural part A is a 6- to 10-member ring, and X 5 R on B and from Z 2 R D Joining to form a multi-ring fused ring system, and X 4 Not N;

[0388] 2) Structural part A is a 5-membered ring, Z 2 It is NR D X 5 R on B and from Z 2 R D Joining to form a multi-ring fused ring system, and X 4 It's not N, the condition is if Z 1 It is BR C Structural part A is imidazole, and X 1 and X 3 If it is N, then by RB and from Z 2 R D The resulting polycyclic fused ring system is neither tetrahydroquinoline nor unsubstituted carbazole;

[0389] 3) Structural part A is a 6-membered ring;

[0390] 4) Structural part A is a 6-membered ring, X 3 It is N, and Z 1 Selected from BR C GaR C SiR C R C’ and GeR C R C’ ;

[0391] 5) Structural part B is a 6-membered ring, X 4 It is N, and Z 1 Selected from BR C GaR C SiR C R C’ and GeR C R C’ The condition is that if Z 2 It is NR D Then R D and from X 5 R B Non-jointing forms a ring;

[0392] 6) Both structural part A and structural part B are 6-membered rings, Z 1 Selected from C=O, C=S, and C=Se, and Z 2 It is NR D The condition is that if M is Ir, then R D It is a cyclic group;

[0393] 7) R A R B R C (If it exists) and R D At least one of them (if present) includes a group selected from germanyl, boranyl and partially or fully deuterated silyl groups;

[0394] 8) R A R B R C (If it exists) and R D At least one of them (if it exists) includes three 6-membered aromatic rings that are not fused together with each other, or an aromatic ring fused with a non-aromatic ring.

[0395] 9) Structural part A is a 5-membered ring and Z 1Selected from C=O, C=S, and C=Se; and

[0396] 10) X 1 and X 3 Both are N, X 2 It is C, and structural part A is an imidazole ring, and the two Rs A They combine to form a benzene ring that is further substituted;

[0397] 11) The compound contains The structure and at least one of the following three conditions is true: (i) at least one R B It is neither hydrogen nor CH3, (ii)X 5 To X 9 At least one of them is N, and (iii)R D It exists and is a heteroaryl group or contains at least one electron-withdrawing group, provided that X 5 To X 9 If both are C, then R C and R D Non-joint formation of a 6-membered ring and R D no or .

[0398] In some embodiments, when structural part E is present, it is a 5- or 6-membered carbocyclic or heterocyclic aromatic ring, X 20 and X 21 Each can be independently represented as C or N, Z 5 For C or N, R E The presence of R indicates monosubstitution up to the maximum permissible substitution, or no substitution. E It is hydrogen or a substituent selected from the following: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silalkyl, germanalkyl, boronalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphin, and combinations thereof.

[0399] In some implementations, when structural part E is absent, then L 1 K does not exist. 3 It's a direct key, R E and X 20 Does not exist, X 21 Selected from BR, BRR', NR, NRR', PR, PRR', P(O)R, O, S, Se, C=O, C=S, C=Se, C=NR, C=CRR', S=O, SO2, CR, CRR', SiRR', and GeRR', and Z 5 Selected from CR, NR, O, S, Se, P and As.

[0400] In some implementations, when structural part F is present, it is a 5- or 6-membered carbocyclic or heterocyclic aromatic ring, X 22 and X 23 Each can be independently represented as C or N, Z 6 For C or N, R F The presence of and indicating monosubstitution up to the maximum permissible substitution, or no substitution, and R E It is hydrogen or a substituent selected from the following: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silalkyl, germanalkyl, boronalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphin, and combinations thereof.

[0401] In some implementations, when structural part F is absent, then L 3 K does not exist. 4 It's a direct key, R F and X 23 Does not exist, X 22 Selected from BR, BRR', NR, NRR', PR, PRR', P(O)R, O, S, Se, C=O, C=S, C=Se, C=NR, C=CRR', S=O, SO2, CR, CRR', SiRR', and GeRR', and Z 6 Selected from CR, NR, O, S, Se, P and As.

[0402] In some embodiments, the compound is essentially composed of Formula II.

[0403] In some embodiments, the compound has the structure of Formula II.

[0404] In some embodiments, the compound comprises a structure of formula IIa or IIb:

[0405] Formula IIa,

[0406] Formula IIb,

[0407] In some embodiments, the compound has the structure of Formula II, with at least one R, R', R α R β R A R B R C R C’ R D R E and R FIt is partially or completely deuterated. In some embodiments, at least one R A It is partially or completely deuterated. In some embodiments, at least one R B It is partially or completely deuterated. In some embodiments, at least one R C It is partially or completely deuterated. In some embodiments, at least one R C’ Partially or completely replaced by deuterium. In some embodiments, at least one R D It is partially or completely deuterated. In some embodiments, at least one R E It is partially or completely deuterated. In some embodiments, at least one R F It is partially or completely deuterated. In some embodiments, at least one R α Or R β It is partially or completely deuterated. In some embodiments, at least one R or R′ is partially or completely deuterated.

[0408] In some embodiments, the compound has the structure of Formula II, with at least one R, R', R α R β R A R B R C R C’ R D R E and R F Selected from generic substituents as defined herein. In some embodiments, at least one R A Selected from generic substituents as defined herein. In some embodiments, at least one R B Selected from generic substituents as defined herein. In some embodiments, at least one R C Selected from generic substituents as defined herein. In some embodiments, at least one R C’ Selected from generic substituents as defined herein. In some embodiments, at least one R D Selected from generic substituents as defined herein. In some embodiments, at least one R E Selected from generic substituents as defined herein. In some embodiments, at least one R F The substituents are selected from those defined herein. In some embodiments, at least one R or R′ is selected from those defined herein. α Or R β Selected from universal substituents as defined in this article.

[0409] In some embodiments, the compound has the structure of Formula II, with at least one R, R', R αR β R A R B R C R C’ R D R E and R F Selected from preferred general substituents as defined herein. In some embodiments, at least one R A Selected from preferred general substituents as defined herein. In some embodiments, at least one R B Selected from preferred general substituents as defined herein. In some embodiments, at least one R C Selected from preferred general substituents as defined herein. In some embodiments, at least one R C’ Selected from preferred general substituents as defined herein. In some embodiments, at least one R D Selected from preferred general substituents as defined herein. In some embodiments, at least one R E Selected from preferred general substituents as defined herein. In some embodiments, at least one R F The substituents are selected from preferred general substituents as defined herein. In some embodiments, at least one R or R′ is selected from preferred general substituents as defined herein. In some embodiments, at least one R α Or R β Selected from preferred general substituents as defined herein.

[0410] In some embodiments, the compound has the structure of Formula II, with at least one R A It is or contains an electron-withdrawing group from an EWG1 LIST as defined herein. In some embodiments, at least one R A It is or contains an electron-withdrawing group from EWG2 LIST as defined herein. In some embodiments, at least one R A It is or contains an electron-withdrawing group from EWG3 LIST as defined herein. In some embodiments, at least one R A It is or contains an electron-withdrawing group from EWG4 LIST as defined herein. In some embodiments, at least one R A It is or contains electron-withdrawing groups from Pi-EWG LIST as defined herein.

[0411] In some embodiments, the compound has the structure of Formula II, with at least one R B It is or contains an electron-withdrawing group from an EWG1 LIST as defined herein. In some embodiments, at least one R BIt is or contains an electron-withdrawing group from EWG2 LIST as defined herein. In some embodiments, at least one R B It is or contains an electron-withdrawing group from EWG3 LIST as defined herein. In some embodiments, at least one R B It is or contains an electron-withdrawing group from EWG4 LIST as defined herein. In some embodiments, at least one R B It is or contains electron-withdrawing groups from Pi-EWG LIST as defined herein.

[0412] In some embodiments, the compound has the structure of Formula II, with at least one R C It is or contains an electron-withdrawing group from an EWG1 LIST as defined herein. In some embodiments, at least one R C It is or contains an electron-withdrawing group from EWG2 LIST as defined herein. In some embodiments, at least one R C It is or contains an electron-withdrawing group from EWG3 LIST as defined herein. In some embodiments, at least one R C It is or contains an electron-withdrawing group from EWG4 LIST as defined herein. In some embodiments, at least one R C It is or contains electron-withdrawing groups from Pi-EWG LIST as defined herein.

[0413] In some embodiments, the compound has the structure of Formula II, with at least one R C’ It is or contains an electron-withdrawing group from an EWG1 LIST as defined herein. In some embodiments, at least one R C’ It is or contains an electron-withdrawing group from EWG2 LIST as defined herein. In some embodiments, at least one R C’ It is or contains an electron-withdrawing group from EWG3 LIST as defined herein. In some embodiments, at least one R C’ It is or contains an electron-withdrawing group from EWG4 LIST as defined herein. In some embodiments, at least one R C’ It is or contains electron-withdrawing groups from Pi-EWG LIST as defined herein.

[0414] In some embodiments, the compound has the structure of Formula II, with at least one R D It is or contains an electron-withdrawing group from an EWG1 LIST as defined herein. In some embodiments, at least one R DIt is or contains an electron-withdrawing group from EWG2 LIST as defined herein. In some embodiments, at least one R D It is or contains an electron-withdrawing group from EWG3 LIST as defined herein. In some embodiments, at least one R D It is or contains an electron-withdrawing group from EWG4 LIST as defined herein. In some embodiments, at least one R D It is or contains electron-withdrawing groups from Pi-EWG LIST as defined herein.

[0415] In some embodiments, the compound has the structure of Formula II, with at least one R E It is or contains an electron-withdrawing group from an EWG1 LIST as defined herein. In some embodiments, at least one R E It is or contains an electron-withdrawing group from EWG2 LIST as defined herein. In some embodiments, at least one R E It is or contains an electron-withdrawing group from EWG3 LIST as defined herein. In some embodiments, at least one R E It is or contains an electron-withdrawing group from EWG4 LIST as defined herein. In some embodiments, at least one R E It is or contains electron-withdrawing groups from Pi-EWG LIST as defined herein.

[0416] In some embodiments, the compound has the structure of Formula II, with at least one R F It is or contains an electron-withdrawing group from an EWG1 LIST as defined herein. In some embodiments, at least one R F It is or contains an electron-withdrawing group from EWG2 LIST as defined herein. In some embodiments, at least one R F It is or contains an electron-withdrawing group from EWG3 LIST as defined herein. In some embodiments, at least one R F It is or contains an electron-withdrawing group from EWG4 LIST as defined herein. In some embodiments, at least one R F It is or contains electron-withdrawing groups from Pi-EWG LIST as defined herein.

[0417] In some implementations, structural part E (if present) and structural part F (if present) are both 6-membered aromatic rings.

[0418] In some implementations, the structural part F (if present) is a 5- or 6-membered heteroaromatic ring.

[0419] In some implementations, L 1 It is O or CRR'.

[0420] In some implementation schemes, Z 5 It is N and Z 6 It's C.

[0421] In some implementation schemes, Z 5 It is C and Z 6 It is N.

[0422] In some implementations, L 2 It is a direct key.

[0423] In some implementations, L 2 It is NR.

[0424] In some implementation schemes, K 3 and K 4 They are all direct keys.

[0425] In some implementation schemes, K 3 and K 4 One of them is O.

[0426] In some embodiments, each of structural portions E and F is independently selected from benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, imidazole-derived carbene, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole, triazole, naphthalene, quinoline, isoquinoline, quinazoline, benzofuran, aza-benzofuran, phenanthro[3,2-b]benzofuran, benzoxazole, aza-benzoxazole, benzothiophene, aza-benzothiophene, benzothiazole, aza- Benzothiazole, benzoselenophenol, aza-benzoselenophenol, indene, aza-indene, indole, aza-indole, benzimidazole, aza-benzimidazole, benzimidazole-derived carbene, aza-benzimidazole-derived carbene, benzobenzimidazole, aza-benzimidazole, carbazole, aza-carbazole, dibenzofuran, aza-dibenzofuran, dibenzothiophene, aza-dibenzothiophene, quinoxaline, phthalazine, phenanthrene, azaphenanthrene, anthracene, azaanthracene, phenanthridine, fluorene, and azafluorene.

[0427] In some embodiments, the compound is selected from compounds having the formula Pt(L A’ (L) y Compounds of:

[0428]

[0429] Where L A’ Selected from L A1’ -1 to L A1’ The structure of -470 is shown in List 10 below:

[0430] , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , ， ， , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , and ;

[0431] Where L y Selected from L y1 -1 to L y1 The structure of -133 is shown below in LIST 13:

[0432] , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , and ;

[0433] Each R X and R Y Independently hydrogen or a substituent selected from the following: deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silalkyl, germanalkyl, boroalkyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thioyl, and combinations thereof.

[0434] The compound of claim 91, wherein R, R', R X R Y R A R B R C R D R E and R F At least one of them is independently selected from the following LIST 11 structure:

[0435] , , , , , , , , , , , , , , , , , , , , , , , , , , , , and ;

[0436] Q A Q B Q C Q D and Q E Each of these terms independently represents a single substitution up to the maximum permissible substitution, or no substitution;

[0437] Each Q A Q B Q C Q D Q E Q A1 Q B1 Q C1 Q D1 and Q E1 Independently hydrogen or a substituent selected from the following: alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boronalkyl, arylalkyl, alkoxy, aryloxy, amino, silalkyl, germanalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphinyl, selenyl, and combinations thereof;

[0438] Each Y aa and Y bbThe compounds are independently selected from direct bonds, BR, BRR', NR, PR, O, S, Se, C=O, C=S, C=Se, C=NR, C=CRR', S=O, SO2, CR, CRR', SiRR', GeRR', alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof; and any two substituents can be joined or fused to form a ring. In some embodiments, the compound is selected from Pt(L) A1’ -1)(L y1 -1) to Pt(L A1’ -470)(L y1 Compounds of -133).

[0439] In some embodiments, the compound is selected from compounds having the formula Pt(L A’ (L) y Compounds of:

[0440]

[0441] Where L A’ Selected from L A’ Q1-(R i (R) j (R) k (R) l ), L A’ Q2-(R j (R) k (R) l) , L A’ Q3-(R j (R) k (R) l (R) m ), L A’ Q4-(R i (R) j (R) k (R) n ), L A’ Q5-(R i (R) k (R) l (R) m ), L A’ Q6-(R k (R) l (R) m (R) o ), L A’ Q7-(R j (R) k (R) n ), L A’ Q8-(R i (R) k) (R l(R) o ), L A’ Q9-(R j (R) l (R) m (R) n Q1 is the integers 1-15, 17-19, 21-27, 29-259, 261, 263-276, 278, 280-366, 367-372, 376, and 396-400; Q2 is 16, 20, 28, 260, 262, 277, 279, 391, and 393; Q3 is the integers 373-375, 378-382, 384, 385, and 401-406; Q4 is 377; Q5 is 383 and 386; Q6 is 387-390 and 394; Q7 is 392; Q8 is 395; Q9 is 407; each i , j , k , m , n , o ,and l Independently, it is an integer from 1 to 468; R i , R j , R k , R l , R m , R n and R o Each of the elements is independently selected from R1 to R468, where R1 to R468 are defined in LIST12, and each L... A’ The structure is defined in the following table (LIST 14):

[0442]

[0443]

[0444]

[0445]

[0446]

[0447]

[0448]

[0449]

[0450]

[0451]

[0452]

[0453]

[0454]

[0455]

[0456]

[0457]

[0458]

[0459]

[0460]

[0461]

[0462]

[0463]

[0464]

[0465]

[0466]

[0467]

[0468]

[0469]

[0470]

[0471]

[0472]

[0473]

[0474]

[0475] Where L y Selected from L y Z1-(R s (R)t )(R u ), L y Z2-(R p )(R q )(R r )(R s ), L y Z3-(R q )(R r )(R s ),L y Z4-(R p )(R q )(R r )(R t ), L y Z5-(R p )(R q )(R r )(R u ), L y Z6-(R q )(R r )(R u ), L y Z7-(R p )(R q )(R s )(R v ), L y Z8-(R q )(R s )(R v ), L y Z9-(R s )(R v )(R t ), L y Z10-(R p )(R q )(R s )(R v )(R t ),L y Z11-(R p )(R s )(R v ), L y Z12-(R p )(R s )(R v )(R tZ1 is an integer from 1 to 95; Z2 is an integer from 96 to 98, 102 to 111, 116, 120, and 121; Z3 is an integer from 99, 113, 117 to 119, and 122; Z4 is 100, 101, and 115; Z5 is 112; Z6 is 114; Z7 is 123 and 124; Z8 is 125; Z9 is 126; Z10 is 127; Z11 is 128 and 129; Z12 is 130; each p, q, r, s, t, u, and v is an independent integer from 1 to 468, R p ,R q , R r , R s , R t , R u and R v Each of them is independently selected from R1 to R468, and each L y The structure is defined in the following table (LIST 15):

[0476]

[0477]

[0478]

[0479]

[0480]

[0481]

[0482]

[0483]

[0484]

[0485]

[0486]

[0487]

[0488]

[0489] R1 to R468 have the following structure (LIST 12):

[0490]

[0491]

[0492]

[0493]

[0494]

[0495]

[0496]

[0497]

[0498]

[0499]

[0500]

[0501]

[0502]

[0503]

[0504]

[0505]

[0506]

[0507]

[0508]

[0509]

[0510]

[0511]

[0512]

[0513] In some embodiments, the compound is selected from the structures in the following LIST 16:

[0514] , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , and .

[0515] In some implementations, L B Selected from substituted or unsubstituted phenylpyridine, substituted or unsubstituted phenylimidazolium, and substituted or unsubstituted phenylbenzimidazole; and L C It is a substituted or unsubstituted acetylacetone compound.

[0516] In some embodiments, the compound comprises an electron-withdrawing group. In some embodiments, the electron-withdrawing group has a Hammett constant greater than 0. In some embodiments, the electron-withdrawing group has a Hammett constant equal to or greater than 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, or 1.1.

[0517] In some embodiments, the compound may have the formula Ir(L A 3. Formula Ir(L) A (L) Bk )2. Equation Ir(L A )2(L Bk ), formula Ir(L A )2(L Cj-I ), formula Ir(L A )2(L Cj-II ), formula Ir(L A (L) Bk (L) Cj-I ) or formula Ir(L A (L) Bk (L) Cj-II ), where L A It is the ligand defined in this paper with respect to formula I; L Bk Defined in this document; and L Cj-I and L Cj-II Each is defined in this article.

[0518] In some embodiments, each of structural part A, structural part B, structural part E, and structural part F may be independently selected from: benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole, triazole, naphthalene, quinoline, isoquinoline, quinazoline, benzofuran, aza-benzofuran, benzoxazole, aza-benzoxazole, benzothiophene Aza-benzothiophene, benzothiazole, aza-benzothiazole, benzoselenene, aza-benzoselenene, indene, aza-indene, indole, aza-indole, benzimidazole, aza-benzimidazole, carbazole, aza-carbazole, dibenzofuran, aza-dibenzofuran, dibenzothiophene, aza-dibenzothiophene, quinoxaline, phthalazine, phenanthrene, azaphenanthrene, anthracene, azaanthracene, phenanthridine, fluorene, and azafluorene.

[0519] In some embodiments, each of structural portion A, structural portion B, structural portion E, and structural portion F can independently be a polycyclic fused ring structure. In some embodiments, each of structural portion A, structural portion B, structural portion E, and structural portion F can independently be a polycyclic fused ring structure comprising at least two fused rings. In some embodiments, the polycyclic fused ring structure has one 6-membered ring and one 5-membered ring. In some such embodiments, the 5-membered or 6-membered ring can be coordinated with a metal. In some embodiments, the polycyclic fused ring structure has two 6-membered rings. In some embodiments, each of structural portion A, structural portion B, structural portion E, and structural portion F can independently be selected from benzofuran, benzothiophene, benzoselenene, naphthalene, and their nitrogen heteropolymorphs.

[0520] In some embodiments, each of structural moiety A, structural moiety B, structural moiety E, and structural moiety F may independently be a polycyclic fused ring structure comprising at least three fused rings. In some embodiments, the polycyclic fused ring structure has two 6-membered rings and one 5-membered ring. In some such embodiments, the 5-membered ring is fused to the ring coordinated to the metal M, and the second 6-membered ring is fused to the 5-membered ring. In some embodiments, each of structural moiety A, structural moiety B, structural moiety E, and structural moiety F may independently be selected from dibenzofuran, dibenzothiophene, dibenzoselenene, and their nitrogen heteromorphs. In some such embodiments, each of structural moiety A, structural moiety B, structural moiety E, and structural moiety F may independently be further substituted at the ortho or meta position of the O, S, or Se atom by a substituent selected from deuterium, fluorine, nitrile, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof. In some such embodiments, the azirmonomorph contains exactly one N atom at the 6-position (ortho to O, S, or Se) and a substituent at the 7-position (meta to O, S, or Se).

[0521] In some embodiments, each of structural portion A, structural portion B, structural portion E, and structural portion F may independently be a polycyclic fused ring structure comprising at least four fused rings. In some embodiments, the polycyclic fused ring structure comprises three 6-membered rings and one 5-membered ring. In some such embodiments, the 5-membered ring is fused to the ring coordinated to the metal M, the second 6-membered ring is fused to the 5-membered ring, and the third 6-membered ring is fused to the second 6-membered ring. In some such embodiments, the third 6-membered ring is further substituted with a substituent selected from deuterium, fluorine, nitriles, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0522] In some embodiments, each of structural portions A, B, E, and F can independently be a multi-ring fused ring structure comprising at least five fused rings. In some embodiments, the multi-ring fused ring structure comprises four 6-membered rings and one 5-membered ring, or three 6-membered rings and two 5-membered rings. In some embodiments comprising two 5-membered rings, the 5-membered rings are fused together. In some embodiments comprising two 5-membered rings, the 5-membered rings are separated by at least one 6-membered ring. In some embodiments having one 5-membered ring, the 5-membered ring is fused with a ring coordinated to metal M, a second 6-membered ring is fused with the 5-membered ring, a third 6-membered ring is fused with the second 6-membered ring, and a fourth 6-membered ring is fused with the third 6-membered ring.

[0523] In some embodiments, each of structural moiety A, structural moiety B, structural moiety E, and structural moiety F may independently be the azirionic form of the aforementioned polycyclic fused ring. In some such embodiments, each of structural moiety A, structural moiety B, structural moiety E, and structural moiety F may independently contain exactly one azirionic N atom. In some such embodiments, at least one of structural moiety A, structural moiety B, structural moiety E, and structural moiety F contains exactly two azirionic N atoms, which may be in one ring or in two different rings. In some such embodiments, the ring having azirionic N atoms is separated from the metal M atom by at least two other rings. In some such embodiments, the ring having azirionic N atoms is separated from the metal M atom by at least three other rings. In some such embodiments, each adjacent position of the azirionic N atom is substituted.

[0524] In some embodiments, a first ligand L comprising Formula I as described herein is used. AThe compound may be at least 30% deuterated, at least 40% deuterated, at least 50% deuterated, at least 60% deuterated, at least 70% deuterated, at least 80% deuterated, at least 90% deuterated, at least 95% deuterated, at least 99% deuterated, or 100% deuterated. As used herein, the percentage of deuteration has its general meaning and includes the percentage of all possible hydrogen atoms (e.g., positions for hydrogen or deuterium) in the compound occupied by deuterium atoms. In some embodiments, the carbon atoms constituting the ring coordinated with metal M are fully or partially deuterated. In some embodiments, the carbon atoms contained in the polycyclic system coordinated with metal M are fully or partially deuterated. In some embodiments, the substituents attached to the ring system of a monocyclic or fused polycyclic ring coordinated with metal M are fully or partially deuterated.

[0525] In some embodiments, the compounds of Formula I emit at room temperature with a full width at half maximum (FWHM) equal to or less than 50, 45, 40, 35, 30, 25, 20, 15, 10, or 5 nm. For OLED display applications, a narrower FWHM implies better color purity.

[0526] In the formula M(L) defined above A ) p (L B ) q (L C ) r In some embodiments of the heteroligand compound, ligand L A Having the first substituent R I The first substituent R I Having the first atom aI, in ligand L A Of all the atoms, the first atom aI is the farthest from the metal M. Additionally, ligand L... B (If present) has a second substituent R II The second substituent R II Having the first atom α-II, in ligand L B Of all the atoms, the first atom a-II is the farthest from the metal M. Furthermore, ligand L... C (If present) has a third substituent R III The third substituent R III Having the first atom α-III, in ligand L C Of all the atoms, the first atom a-III is the farthest from metal M.

[0527] In such heterocomplexes, vector V D1 V D2 and V D3 It can be defined as follows. V D1Let V represent the direction from metal M to the first atom aI, and let V be the vector. D1 The value of D 1 Represents metal M and first substituent R I The straight-line distance between the first atoms aI in V. D2 This represents the direction from metal M to the first atom a-II, and the vector V D2 The value of D 2 Represents metal M and second substituent R II The straight-line distance between the first atom a-II in V. D3 This represents the direction from metal M to the first atom a-III, and the vector V D3 The value of D 3 Represents metal M and third substituent R III The straight-line distance between the first atom a-III in the matrix.

[0528] In such heterocomplexes, a sphere of radius r is defined, with metal M at its center, and radius r is the radius that allows the sphere to surround non-substituents R in the compound. I R II and R III The minimum radius of all atoms in a portion; and where D 1 D 2 and D 3 At least one of them is at least 1.5 Å larger than the radius r. In some embodiments, D 1 D 2 and D 3 At least one of them is at least 2.9, 3.0, 4.3, 4.4, 5.2, 5.9, 7.3, 8.8, 10.3, 13.1, 17.6, or 19.1 Å larger than the radius r. In some embodiments, D 1 D 2 and D 3 At least two of them are at least 1.5, 2.9, 3.0, 4.3, 4.4, 5.2, 5.9, 7.3, 8.8, 10.3, 13.1, 17.6 or 19.1 Å larger than the radius r.

[0529] In some embodiments of such a heteropolymer compound, the compound has a transition dipole moment axis, and the transition dipole moment axis is related to the vector V. D1 V D2 and V D3 The angle between them is defined, where the transition dipole moment axis and the vector V are intersected. D1 V D2 and V D3 At least one of the angles between them is less than 40°. In some embodiments, the transition dipole moment axis is related to the vector V. D1 VD2 and V D3 At least one of the angles between them is less than 30°, 20°, 15°, or 10°. In some embodiments, the transition dipole moment axis is related to the vector V. D1 V D2 and V D3 At least two of the angles between them are less than 20°. In some implementations, the transition dipole moment axis is related to the vector V. D1 V D2 and V D3 At least two of the angles between them are less than 15° or 10°.

[0530] In some implementations, the transition dipole moment axis is related to the vector V. D1 V D2 and V D3 All three angles between them are less than 20°. In some implementations, the transition dipole moment axis is parallel to the vector V. D1 V D2 and V D3 All three angles between them are less than 15° or 10°.

[0531] In some embodiments of such heteropolymer compounds, the compound has a vertical dipole ratio (VDR) of 0.33 or less. In some embodiments of such heteropolymer compounds, the compound has a VDR of 0.30, 0.25, 0.20, or 0.15 or less.

[0532] Those skilled in the art will readily understand the meaning of the terms "transition dipole moment axis" and "vertical dipole ratio" of the compound. However, the meanings of these terms can be found in U.S. Patent 10,672,997, the disclosure of which is incorporated herein by reference in its entirety. In U.S. Patent 10,672,997, the horizontal dipole ratio (HDR) of the compound is discussed, not the VDR. However, those skilled in the art will readily understand that VDR = 1 - HDR.

[0533] In some embodiments, the compound may be an emission dopant. In some embodiments, the compound may generate emission via phosphorescence, fluorescence, thermally activated delayed fluorescence, triplet-triplet annihilation, or a combination of these processes. In some embodiments, the emission dopant may be a racemic mixture or may be enriched with one enantiomer. In some embodiments, the compound of the present invention may have different stereoisomers, such as fac and mer. The compound of the present invention relates both to a single isomer and to mixtures of various isomers in any mixing ratio. In some embodiments, the compound may be homogamic (each ligand is identical). In some embodiments, the compound may be heterogamic (at least one ligand is different from the others). When more than one ligand is coordinated to a metal, in some embodiments, the ligands may all be identical. In some other embodiments, at least one ligand is different from the others. In some embodiments, each ligand may be different from every other ligand. This is also true in embodiments where the ligand coordinated to the metal may be linked to other ligands coordinated to the metal to form tridentate, tetradentate, pentadentate, or hexadentate ligands. Therefore, in some embodiments where ligands are linked together, all ligands may be the same, while in other embodiments, at least one of the linked ligands may be different from the others.

[0534] In another aspect of this disclosure, compositions comprising the novel compounds disclosed herein are described. The compositions may include one or more components selected from: solvents, emitters, hosts, hole injection materials, hole transport materials, electron blocking materials, hole blocking materials, and electron transport materials, as disclosed herein.

[0535] This disclosure covers any chemical structure of novel compounds comprising this disclosure, or in their neutral molecular form, or in their monovalent or multivalent form, or in their monomeric or polymeric form, or in their macromolecular or supramolecular form; wherein said compounds have a first ligand L of Formula I as described herein. A In another aspect, this disclosure also provides compositions of compounds of formula I, wherein the compounds of formula I comprise their neutral molecular form, their monovalent or multivalent form, their monomeric or polymeric form, or their macromolecular or supramolecular form; and wherein said compound has a first ligand L of formula I as described herein. AAs used herein, a "monovalent variant of a compound" refers to the same structural moiety as the compound, except that one hydrogen atom has been removed and replaced by a bond attached to the remainder of the chemical structure. As used herein, a "multivalent variant of a compound" refers to the same structural moiety as the compound, except that more than one hydrogen atom has been removed and replaced by one or more bonds attached to the remainder of the chemical structure. In the case of supramolecular structures, the compounds of the present invention can also be incorporated into supramolecular complexes without covalent bonds. As used herein, the description of structure A containing structural moiety B means that structure A includes the structure of structural moiety B, excluding any H or D atoms that can be attached to structural moiety B. This is because at least one H or D atom on the structure of a given structural moiety must be substituted to become a substituent, such that structural moiety B can be part of structure A, and once part of structure A, one or more H or D atoms on the structure of a given structural moiety B can be further substituted.

[0536] In some implementation schemes, R, R', R α R β R A R B R C R D R E Or R F At least one of them is partially or completely deuterated. In some embodiments, at least one R A It is partially or completely deuterated. In some embodiments, at least one R B It is partially or completely deuterated. In some embodiments, at least one R C It is partially or completely deuterated. In some embodiments, at least one R D It is partially or completely deuterated. In some embodiments, at least one R E It is partially or completely deuterated. In some embodiments, at least one R F It is partially or completely deuterated. In some embodiments, at least one of R or R' is partially or completely deuterated. In some embodiments, R α Or R β At least one of them is partially or completely deuterated.

[0537] In some implementation schemes, R, R', R α R β R A R B R C R D R E Or R FAt least one of R or R' is a substituent selected from universal substituents as defined herein. In some embodiments, at least one of R or R' is selected from universal substituents as defined herein. In some embodiments, R α Or R β At least one of them is selected from universal substituents as defined herein. In some embodiments, at least one R A Selected from generic substituents as defined herein. In some embodiments, at least one R B Selected from generic substituents as defined herein. In some embodiments, at least one R C Selected from generic substituents as defined herein. In some embodiments, at least one R D Selected from generic substituents as defined herein. In some embodiments, at least one R E Selected from generic substituents as defined herein. In some embodiments, at least one R F Selected from universal substituents as defined in this article.

[0538] In some implementation schemes, R, R', R α R β R A R B R C R D R E Or R F At least one of R or R' is a substituent selected from preferred universal substituents as defined herein. In some embodiments, at least one of R or R' is selected from preferred universal substituents as defined herein. In some embodiments, R α Or R β At least one of them is selected from preferred general substituents as defined herein. In some embodiments, at least one R A Selected from preferred general substituents as defined herein. In some embodiments, at least one R B Selected from preferred general substituents as defined herein. In some embodiments, at least one R C Selected from preferred general substituents as defined herein. In some embodiments, at least one R D Selected from preferred general substituents as defined herein. In some embodiments, at least one R E Selected from preferred general substituents as defined herein. In some embodiments, at least one R F Selected from preferred general substituents as defined herein.

[0539] C. OLEDs and devices disclosed herein

[0540] In another aspect, this disclosure also provides an OLED device comprising a first organic layer containing compounds as disclosed in the foregoing compound section of this disclosure.

[0541] In some embodiments, an OLED includes: an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises a compound described herein.

[0542] In some embodiments, the organic layer is selected from the group consisting of HIL, HTL, EBL, EML, HBL, ETL, and EIL. In some embodiments, the organic layer may be an emission layer and the compound as described herein may be an emission dopant or a non-emission dopant. In some embodiments, the emission layer may also optionally contain a dopant selected from the group consisting of delayed-fluorescence and non-delayed-fluorescence types.

[0543] In some embodiments, the organic layer may further comprise a body, wherein the body comprises at least one chemical group selected from the group consisting of: triphenylene, carbazole, indolocarbazole, dibenzothiophene, dibenzofuran, dibenzoselenene, 5λ 2 -Benzo[d]benzo[4,5]imidazo[3,2-a]imidazolium, 5,9-dioxa-13b-boronazona[3,2,1-de]anthracene, azacyclohexylborane, oxaborane, dihydroacrylidine, oxanthracene, dihydrobenzoazasilane, dibenzooxasilane, phenoxazine, phenoxthiazine, dihydrophenazine, fluorene, naphthalene, anthracene, phenanthrene, phenanthroline, benzoquinoline, quinoline, isoquinoline, quinazoline, pyrimidine, pyrazine, pyridine, triazine, borane, silane, aza-triphenylene, aza-carbazole, aza-indolocarbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, aza-5λ 2 - benzo[d]benzo[4,5]imidazo[3,2-a]imidazo and aza-(5,9-dioxa-13b-boronanaphtho[3,2,1-de]anthracene).

[0544] In some embodiments, the subject may be selected from a group consisting of the following subject group 1 (HOST Group 1):

[0545] , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , and ,

[0546] in:

[0547] Each of J1 to J6 is independently either C or N;

[0548] L' is a direct bond or an organic linking group;

[0549] Each Y AA Y BB Y CC and Y DD Independently select from the following groups: non-existent bond, direct bond, O, S, Se, CRR', SiRR', GeRR', NR, BR, BRR';

[0550] R A' R B' R C' R D' R E' R F' and R G' Each of these terms independently represents monosubstituted, at most maximum substituted, or unsubstituted.

[0551] Each R, R', R A' R B' R C' R D' R E' R F' and R G' Substituents are independently hydrogen or selected from the group of general substituents as defined herein; any two substituents may join or fuse to form a ring;

[0552] Furthermore, where possible, each unsubstituted aromatic carbon atom can be replaced by one or more N atoms to form a nitrogen-substituted ring.

[0553] In some embodiments, at least one of J1 to J3 is N. In some embodiments, at least two of J1 to J3 are N. In some embodiments, all three of J1 to J3 are N. In some embodiments, each Y CC and Y DD Independently, it is O, S, or SiRR', or more preferably O or S. In some embodiments, at least one unsubstituted aromatic carbon atom is substituted with N to form a nitrogen heterocycle.

[0554] In some embodiments, the subject is selected from the group consisting of: EG1-MG1-EG1 to EG53-MG27-EG53 having the formula EGa-MGb-EGc, or EG1-EG1 to EG53-EG53 having the formula EGa-EGc when MGb is absent, where a is an integer from 1 to 53, b is an integer from 1 to 27, and c is an integer from 1 to 53. The structures of EG1 to EG53 are shown below:

[0555] , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , .

[0556] The structural diagrams of MG1 through MG27 are shown below:

[0557] , , , , , , , , , , , , , , , , , , , , , , , , , , .

[0558] In the MGb structure shown above, the two bond positions in the asymmetric structures MG10, MG11, MG12, MG13, MG14, MG17, MG24 and MG25 are marked with numbers for identification purposes.

[0559] In some embodiments, the subject can be any of its nitrogen-substituted variants, its fully or partially deuterated variants, and combinations thereof. In some embodiments, the subject has the formula EGa-MGb-EGc and is selected from the group consisting of h1 to h112 as defined in the following list of subjects group 2, wherein each of MGb, EGa, and EGc is defined as follows:

[0560]

[0561] In the table above, the EGa and EGc structures bonded to one of the asymmetric structures MG10, MG11, MG12, MG13, MG14, MG17, MG24 and MG25 are marked with a numerical prefix, which indicates their bond position in the MGb structure.

[0562] In some embodiments, the organic layer may further comprise a body, wherein the body comprises a metal complex.

[0563] In some embodiments, the emitter layer may comprise two bodies: a first body and a second body. In some embodiments, the first body is a hole transport body and the second body is an electron transport body. In some embodiments, the first body is a hole transport body and the second body is a bipolar body. In some embodiments, the first body is an electron transport body and the second body is a bipolar body. In some embodiments, the first body and the second body may form an excimer complex. In some embodiments, the emitter layer may comprise a third body. In some embodiments, the third body is selected from the group consisting of: an insulating body (wide bandgap body), a hole transport body, and an electron transport body. In some embodiments, the third body forms an excimer complex with one of the first body and the second body, or with both of the first body and the second body. In some embodiments, the emitter layer may comprise a fourth body. In some embodiments, the fourth body is selected from the group consisting of: an insulating body (wide bandgap body), a hole transport body, and an electron transport body. In some embodiments, the fourth body forms an excimer complex with one of the first body, the second body, and the third body, with two of the first body, the second body, and the third body, or with each of the first body, the second body, and the third body. In some embodiments, the LUMO of the electron transport host is less than -2.4 eV, less than -2.5 eV, less than -2.6 eV, or less than -2.7 eV. In some embodiments, the HOMO of the hole transport host is greater than -5.6 eV, greater than -5.5 eV, greater than -5.4 eV, or greater than -5.35 eV. HOMO and LUMO values ​​can be determined using solution electrochemistry. Solution cyclic voltammetry and differential pulse voltammetry can be performed using a CH instrument model 6201B potentiostat, using anhydrous dimethylformamide (DMF) solvent and tetrabutylammonium hexafluorophosphate as the supporting electrolyte. Glassy carbon, platinum wire, and silver wire are used as the working electrode, counter electrode, and reference electrode, respectively. The electrochemical potential can be referenced to the internal ferrocene-ferrocene redox pair (Fc / Fc+) by measuring the peak potential difference using differential pulse voltammetry.According to the literature ((a) Fink, R.; Heischkel, Y.; Thelakkat, M.; Schmidt, H.-W., Chem. Mater. 1998, 10, 3620-3625; (b) Pommerehne, J.; Vestweber, H.; Guss, W.; Mahrt, RF; Bassler, H.; Porsch, M.; Daub, Journal of Advanced Materials 1995, 7, 551), by comparing the redox potentials of the cations and anions with a ferrocene reference (4.8). The corresponding highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energies were determined by measuring the energy of the HOMO (highest occupied molecular orbital) relative to vacuum (eV).

[0564] In some embodiments, the compound described herein may be a sensitizer or a component of a sensitizer; wherein the device may further include a receptor that receives energy from the sensitizer. In some embodiments, the receptor is an emitter in the device. In some embodiments, the receptor may be a fluorescent material. In some embodiments, the compound described herein may be used as a phosphorescent sensitizer in an OLED, wherein one or more layers in the OLED contain receptors in the form of one or more non-delayed fluorescence and / or delayed fluorescence materials. In some embodiments, the compound described herein may be used as a component of an excimer complex used as a sensitizer. As a phosphorescent sensitizer, the compound must be able to transfer energy to the receptor and the receptor to emit energy or further transfer energy to the final emitter. The receptor concentration may range from 0.001% to 99.9%. The receptor may be in the same layer as the phosphorescent sensitizer or in one or more different layers. In some embodiments, the receptor is a thermally activated delayed fluorescence (TADF) material. In some embodiments, the receptor is a non-delayed fluorescence material. In some embodiments, emission may be generated by any one or all of the sensitizer, receptor, and final emitter. In some embodiments, the receptor emits at room temperature with a full width at half maximum (FWHM) equal to or less than 50, 45, 40, 35, 30, 25, 20, 15, 10, or 5 nm. A narrower FWHM means better color purity for OLED display applications.

[0565] As used herein, phosphorescence generally refers to photon emission when the electron spin quantum number changes, that is, the initial and final states of emission have different electron spin quantum numbers, such as from T1 to S0. Most Ir and Pt complexes currently used in OLEDs are phosphorescent emitters. In some embodiments, such exciton complexes can also emit phosphorescence if exciton complex formation involves a triplet emitter. On the other hand, fluorescent emitters generally refer to photon emission when the electron spin quantum number remains constant, such as from S1 to S0 or from D1 to D0. Fluorescent emitters can be delayed or non-delayed fluorescent emitters. Depending on the spin state, fluorescent emitters can be singlet, doublet, or other multiplyt emitters. It is believed that the internal quantum efficiency (IQE) of fluorescent OLEDs can exceed the 25% spin statistical limit through delayed fluorescence. There are two types of delayed fluorescence: P-type and E-type delayed fluorescence. P-type delayed fluorescence is generated by triplet-triplet annihilation (TTA). On the other hand, E-type delayed fluorescence does not depend on the collision of two triplet states, but rather on the thermal population between the triplet and singlet excited states. Thermal energy can activate the triplet state to transition back to the singlet state. This type of delayed fluorescence is also known as TADF. E-type delayed fluorescence characteristics can be seen in excimer complex systems or single compounds. Without being bound by theory, it is assumed that TADF emission requires a small singlet-triplet bandgap (ΔE) less than or equal to 400, 350, 300, 250, 200, 150, 100, or 50 meV. S-T A TADF emitter is a compound or excitocomplex containing electrons. There are two main types of TADF emitters: one called donor-acceptor TADF and the other called multi-resonant (MR) TADF. Typically, a single-compound donor-acceptor TADF compound is constructed by connecting an electron donor moiety (such as an amino or carbazole derivative) and an electron acceptor moiety (such as an N-containing six-membered aromatic ring or a cyano-substituted aromatic ring). Donor-acceptor excitocomplexes can be formed between hole-transporting compounds and electron-transporting compounds. Examples of MR-TADF materials include highly conjugated fused-ring systems. In some embodiments, MR-TADF materials contain boron, carbon, and nitrogen atoms. Such materials may also contain other atoms, such as oxygen. In some embodiments, the reverse intersystem crossing time from T1 to S1 for delayed fluorescence emission at 293 K is less than or equal to 10 microseconds. In some embodiments, such a time can be greater than 10 microseconds and less than 100 microseconds.

[0566] In some embodiments, the OLED may include additional compounds selected from the group consisting of: non-delayed fluorescent materials, delayed fluorescent materials, phosphorescent materials, and combinations thereof.

[0567] In some embodiments, the compounds of the present invention described herein are phosphorescent materials.

[0568] In some embodiments, the phosphorescent material is an emitter that emits light within the OLED. In some embodiments, the phosphorescent material does not emit light within the OLED. In some embodiments, the phosphorescent material transfers its excited state to another material within the OLED. In some embodiments, the phosphorescent material participates in charge transport within the OLED. In some embodiments, the phosphorescent material is a sensitizer or a component of a sensitizer, and the OLED further includes an acceptor. In some embodiments, the phosphorescent material forms an excimer complex with another material within the OLED (e.g., a host material, an emitter material).

[0569] In some embodiments, the non-delayed fluorescent material or the delayed fluorescent material is an emitter that emits light within the OLED. In some embodiments, the non-delayed fluorescent material or the delayed fluorescent material does not emit light within the OLED. In some embodiments, the non-delayed fluorescent material or the delayed fluorescent material transfers its excited state to another material within the OLED. In some embodiments, the non-delayed fluorescent material or the delayed fluorescent material participates in charge transport within the OLED. In some embodiments, the non-delayed fluorescent material or the delayed fluorescent material is an acceptor, and the OLED further includes a sensitizer.

[0570] In some embodiments of OLEDs, the delayed fluorescence material comprises at least one donor group and at least one acceptor group. In some embodiments, the delayed fluorescence material is a metal complex. In some embodiments, the delayed fluorescence material is a non-metallic complex. In some embodiments, the delayed fluorescence material is a Pt, Pd, Zn, Cu, Ag, or Au complex (some of which are also referred to as metal-assisted (MA) TADF). In some embodiments, the metal-assisted delayed fluorescence material comprises a metal-carbamate bond. In some embodiments, the non-delayed fluorescence material or the delayed fluorescence material comprises at least one chemical group selected from the group consisting of: arylamine, aryloxy, arylthio, triphenylene, carbazole, indolocarbazole, dibenzothiophene, dibenzofuran, dibenzoselenene, 5λ 2 -Benzo[d]benzo[4,5]imidazo[3,2-a]imidazo, 5,9-dioxa-13b-boronazona[3,2,1-de]anthracene, 5λ λ diaza Boron-naphthalene Anthracene Oxygen λ 2-aza-13b-boronazona[3,2,1-de]anthracene, azacyclohexylborane, oxaborane, dihydroacridine, oxanthracene, dihydrobenzoazasilane, dibenzooxasilane, phenoxazine, phenoxthiazine, dihydrophenazine, fluorene, naphthalene, anthracene, phenanthrene, phenanthroline, benzoquinoline, quinoline, isoquinoline, quinazoline, pyrimidine, pyrazine, pyridine, triazine, borane, amino, silane, their aza variants and combinations thereof. In some embodiments, the non-delayed fluorescent material or the delayed fluorescent material comprises tri(aryl / heteroaryl)borane, wherein one or more pairs of substituents from the aryl / heteroaryl group are bonded to form a ring. In some embodiments, the fluorescent material comprises at least one chemical group selected from the group consisting of: naphthalene, anthracene, phenanthrene, fluorene, pyrene, β, perylene, and azulene.

[0571] In another aspect, the OLED of this disclosure may also include an emitting region comprising a compound or composition of compounds as disclosed in the foregoing compound section of this disclosure. In some embodiments, the emitting region may comprise a compound or composition of compounds as described herein. In some embodiments, the emitting region comprises one or more organic layers, at least one of said one or more organic layers having a minimum thickness selected from the group consisting of: 350, 400, 450, 500, 550, 600, 650, and 700 Å. In some embodiments, at least one of said one or more organic layers is formed by an emitting system having a figure of merit (FOM) equal to or greater than a value selected from the group consisting of: 2.50, 2.55, 2.60, 2.65, 2.70, 2.75, 2.80, 2.85, 2.90, 2.95, 3.00, 5.00, 10.0, 15.0, and 20.0. The definition of FOM is available in U.S. Patent Application Publication No. 2023 / 0292605, the entire contents of which are incorporated herein by reference. In some embodiments, at least one of the one or more organic layers comprises a compound or a composition of compounds as disclosed in Parts A and D of this disclosure.

[0572] In some embodiments, the OLED or emitting region comprising the compound of the present invention disclosed herein may be incorporated into a full-color pixel arrangement of a device. Such a full-color pixel arrangement of a device comprises at least one pixel, wherein the at least one pixel comprises a first sub-pixel and a second sub-pixel. The first sub-pixel comprises a first OLED, which comprises a first emitting region. The second sub-pixel comprises a second OLED, which comprises a second emitting region. In some embodiments, the first and / or second OLEDs, the first and / or second emitting regions may be the same or different and may each independently have various device features and embodiments comprising the compound of the present invention, as well as various combinations and sub-combinations of various device features and embodiments comprising the compound of the present invention, as disclosed herein.

[0573] In some embodiments, the first emission region is configured to emit light with a peak wavelength λ. max1 The second emission region is configured to emit light with a peak wavelength λ. max2 The light. In some embodiments, the peak wavelength λ max1 With λ max2 The difference between them is at least 4 nm but within the same color. For example, light blue and dark blue light as described above. In some embodiments, the first emission region is configured to emit light with a peak wavelength λ in one region of the visible spectrum at 400-500 nm, 500-600 nm, or 600-700 nm. max1 The light emitted; and the second emission region is configured to emit light having a peak wavelength λ in one of the remaining regions of the visible spectrum: 400-500 nm, 500-600 nm, or 600-700 nm. max2 The light emitted. In some embodiments, the first emitting region comprises (if more than one) a first number of emitting layers deposited on top of another; and the second emitting region comprises (if more than one) a second number of emitting layers deposited on top of another; and the first number is different from the second number. In some embodiments, both the first emitting region and the second emitting region comprise phosphorescent materials that may be the same or different. In some embodiments, the first emitting region comprises phosphorescent material, while the second emitting region comprises fluorescent material. In some embodiments, both the first emitting region and the second emitting region comprise fluorescent materials that may be the same or different.

[0574] In some embodiments, at least one pixel of an OLED or emitting region comprises a total of N sub-pixels; wherein the N sub-pixels include a first sub-pixel and a second sub-pixel; wherein each of the N sub-pixels includes an emitting region; wherein the total number of emitting regions within at least one pixel is equal to or less than N-1. In some embodiments, the second emitting region is identical to the first emitting region; and each sub-pixel of at least one pixel includes an emitting region identical to the first emitting region. In some embodiments, a full-color pixel arrangement may have multiple pixels including a first pixel region and a second pixel region; wherein at least one display feature in the first pixel region differs from a corresponding display feature in the second pixel region, and wherein the at least one display feature is selected from the group consisting of: resolution, cavity mode, color, external coupling, and color filter.

[0575] In some embodiments, the OLED is a stacked OLED comprising one or more charge generating layers (CGLs). In some embodiments, the OLED comprises a first electrode, a first emitting region disposed above the first electrode, a first CGL disposed above the first emitting region, a second emitting region disposed above the first CGL, and a second electrode disposed above the second emitting region. In some embodiments, the first emitting region and / or the second emitting region may have various device features as described above for pixelation devices. In some embodiments, the stacked OLED is configured to emit white. In some embodiments, one or more of the emitting regions in the pixelated OLED or the stacked OLED comprise a sensitizer and an acceptor having various sensitization device features and various embodiments of the compounds of the invention disclosed herein. For example, the first emitting region is included in a sensitization device while the second emitting region is not included in a sensitization device; in some cases, both the first and second emitting regions are included in a sensitization device.

[0576] In some embodiments, the OLED can emit light from at least 1%, 5%, 10%, 30%, 50%, 70%, 80%, 90%, 95%, 99%, or 100% of plasmonic modes. In some embodiments, at least one of an anode, a cathode, or a novel layer disposed immediately adjacent to the anode or cathode serves as a reinforcement layer. The reinforcement layer comprises a plasmonic material exhibiting surface plasmon resonance, the plasmonic material being nonradiatively coupled to the emitter material and transferring excited-state energy from the emitter material to the nonradiative modes of surface plasmon polaritons. In some embodiments, the reinforcement layer is positioned at a distance from the organic emitter layer not exceeding a threshold distance, wherein, due to the presence of the reinforcement layer, the emitter material has a total nonradiative decay rate constant and a total radiative decay rate constant. The threshold distance is the position where the total nonradiative decay rate constant equals the total radiative decay rate constant. Another threshold distance is the distance at which the total radiative decay rate constant divided by the sum of the total nonradiative decay rate constant and the total radiative decay rate constant equals the photoluminescence yield of the emitter material without the reinforcement layer.

[0577] In some embodiments, the OLED further includes an external coupling layer. In some embodiments, the external coupling layer is disposed above the enhancement layer on the side opposite the organic emitting layer. The external coupling layer scatters energy from surface plasmon polaritons. In some embodiments, this energy is scattered as photons into free space. In other embodiments, energy is scattered from the surface plasmon polariton modes of the device into other modes, such as, but not limited to, organic waveguide modes, substrate modes, or another waveguide mode. In some embodiments, one or more intermediary layers may be disposed between the enhancement layer and the external coupling layer. Examples of intermediary layers may be dielectric materials, including organic, inorganic, perovskite, and oxide materials, and may include stacks and / or mixtures of these materials.

[0578] The enhancement layer alters the effective properties of the medium in which the emitter material resides, thereby causing any or all of the following: reduced emissivity, altered emission profile, changes in emission intensity with angle, altered emitter material stability, altered OLED efficiency, and reduced roll-off efficiency of the OLED device. Placing the enhancement layer on the cathode side, anode side, or both sides, or placing the enhancement layer itself as a CGL, produces an OLED device that utilizes any of the aforementioned effects. In addition to the specific functional layers mentioned herein and illustrated in the various OLED examples shown in the figures, the OLED according to this disclosure may also include any other functional layers commonly found in OLEDs.

[0579] In some embodiments, the reinforcing layer may comprise a plasmonic material, an optically active metamaterial, or a hyperbolic metamaterial. In some embodiments, the plasmonic material comprises at least one metal. In such embodiments, the metal may comprise at least one of the following: Ag, Al, Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ru, Pd, In, Bi, or Ca, alloys or mixtures of these materials, and stacks of these materials. In some embodiments, the reinforcing layer is configured as a planar layer. In other embodiments, the reinforcing layer is characterized by wavelengths arranged periodically, quasi-periodically, or randomly, or by subwavelengths arranged periodically, quasi-periodically, or randomly.

[0580] In some embodiments, the outer coupling layer has a wavelength or subwavelength characteristic of being arranged periodically, quasi-periodically, or randomly. In some embodiments, the outer coupling layer may be composed of a plurality of nanoparticles. In some embodiments, the outer coupling layer is composed of a plurality of nanoparticles disposed on a material. In these embodiments, the outer coupling layer can be adjusted by at least one of the following: changing the size of the plurality of nanoparticles, changing the shape of the plurality of nanoparticles, changing the material of the plurality of nanoparticles, adjusting the thickness of the material, changing the refractive index of the material, adding an additional layer disposed on the plurality of nanoparticles, changing the thickness of a reinforcing layer, or changing the material of a reinforcing layer. The plurality of nanoparticles of the device may be formed from at least one of the following: metal, dielectric material, semiconductor material, metal alloy, mixture of dielectric materials, stack or layer of one or more materials and / or a core of one type of material coated with a shell of another type of material. In some embodiments, the outer coupling layer is composed of at least metal nanoparticles, wherein the metal is selected from the group consisting of: Ag, Al, Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ru, Pd, In, Bi, and Ca, alloys or mixtures of these materials, and stacks of these materials. In some embodiments, the outer coupling layer is formed by photolithography.

[0581] In some embodiments of the plasmonic device, the emitter and / or host compound used in the emitter layer has a vertical dipole ratio (VDR) of 0.33 or greater. In some such embodiments, the emitter and / or host compound has a VDR of 0.40, 0.50, 0.60, 0.70 or greater.

[0582] In another aspect, this disclosure also provides a consumer product comprising an organic light-emitting device (OLED) having an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer may comprise compounds or formulations of compounds as disclosed in the foregoing compound section of this disclosure.

[0583] In some embodiments, a consumer product includes an OLED having an anode, a cathode, and an organic layer disposed between the anode and the cathode, wherein the organic layer may contain compounds as described herein.

[0584] Generally, an OLED comprises at least one organic layer disposed between and electrically connected to both the anode and cathode. When a current is applied, holes are injected into the anode and electrons into the organic layer from the cathode. The injected holes and electrons migrate toward their respective oppositely charged electrodes. When electrons and holes are localized on the same molecule, "excitons" are formed, which are localized electron-hole pairs with excited energy states. When excitons relax through photoemission mechanisms, light is emitted. In some cases, excitons can be localized as excimers or excitokines. Non-radiative mechanisms (such as thermal relaxation) may also occur, but are generally considered undesirable.

[0585] Figure 1 An organic light-emitting device 100 is shown. The figures are not necessarily drawn to scale. Device 100 may include a substrate 110, an anode 115, a hole injection layer (HIL) 120, a hole transport layer (HTL) 125, an electron blocking layer (EBL) 130, an emission layer (EML) 135, a hole blocking layer (HBL) 140, an electron transport layer (ETL) 145, an electron injection layer (EIL) 150, a protective layer 155, a cathode 160, and a blocking layer 170. The cathode 160 is a composite cathode having a first conductive layer 162 and a second conductive layer 164. Device 100 can be fabricated by sequentially depositing the layers. The properties and functions of these various layers, as well as the example materials, are described in more detail in columns 6-10 of US 7,279,704, which is incorporated herein by reference.

[0586] Further examples of each of these layers are available. For instance, a flexible and transparent substrate-anode combination is disclosed in U.S. Patent No. 5,844,363, which is incorporated herein by reference in its entirety. An example of a p-doped hole transport layer is m-MTDATA doped with F4-TCNQ in a 50:1 molar ratio, as disclosed in U.S. Patent Application Publication No. 2003 / 0230980, which is incorporated herein by reference in its entirety. Examples of luminescent and host materials are disclosed in U.S. Patent No. 6,303,238 to Thompson et al., which is incorporated herein by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li in a 1:1 molar ratio, as disclosed in U.S. Patent Application Publication No. 2003 / 0230980, which is incorporated herein by reference in its entirety. Examples of cathodes, comprising composite cathodes having a thin layer of metal (e.g., Mg:Ag) having an overlying transparent, conductive, sputtered ITO layer, are disclosed in their entirety in U.S. Patent Nos. 5,703,436 and 5,707,745, which are incorporated herein by reference in their entirety. Theories and uses of barrier layers are described in more detail in U.S. Patent No. 6,097,147 and U.S. Patent Application Publication No. 2003 / 0230980, which are incorporated herein by reference in their entirety. Examples of implantation layers are provided in U.S. Patent Application Publication No. 2004 / 0174116, which is incorporated herein by reference in its entirety. Descriptions of protective layers can be found in U.S. Patent Application Publication No. 2004 / 0174116, which is incorporated herein by reference in its entirety.

[0587] Figure 2 An inverted OLED 200 is shown. The device includes a substrate 210, a cathode 215, an emitter layer 220, a hole transport layer 225, and an anode 230. The device 200 can be fabricated by sequentially depositing these layers. Because the most common OLED configuration has a cathode disposed above the anode, and the device 200 has a cathode 215 disposed below the anode 230, the device 200 can be referred to as an "inverted" OLED. Materials similar to those described with respect to device 100 can be used in the corresponding layers of the device 200. Figure 2 Provide an example of how some layers can be omitted from the structure of device 100.

[0588] Figure 1 and 2The simple layered structures described herein are provided by way of non-limiting examples, and it should be understood that embodiments of this disclosure can be used in conjunction with a variety of other structures. The specific materials and structures described are exemplary in nature, and other materials and structures can be used. Functional OLEDs can be obtained by combining the various layers described in different ways, or the layers can be omitted entirely based on design, performance, and cost factors. Other layers not specifically described may also be included. Materials other than those specifically described may be used. Although many examples provided herein describe various layers as comprising a single material, it should be understood that combinations of materials, such as mixtures of host and dopant, or more generally, mixtures, can be used. Furthermore, the layers may have various sublayers. The names given to the various layers herein are not intended to be strictly limiting. For example, in device 200, hole transport layer 225 transports holes and injects holes into emitter layer 220, and can be described as a hole transport layer or a hole injection layer. In one embodiment, an OLED may be described as having an “organic layer” disposed between a cathode and an anode. This organic layer may comprise a single layer, or may further comprise, for example, regarding Figure 1 and 2 Multiple layers of the different organic materials mentioned above.

[0589] Structures and materials not specifically described can also be used, such as OLEDs (PLEDs) containing polymeric materials, as disclosed in, for example, U.S. Patent No. 5,247,190 to Friend et al., which is incorporated herein by reference in its entirety. By another example, OLEDs with a single organic layer can be used. OLEDs can be stacked, for example as described in, for example, U.S. Patent No. 5,707,745 to Forrest et al., which is incorporated herein by reference in its entirety. OLED structures can deviate from... Figure 1 and 2 The simple layered structure described herein. For example, the substrate may include angled reflective surfaces to improve out-coupling, such as the tabletop structure described in U.S. Patent No. 6,091,195 to Forrest et al., and / or the recessed structure described in U.S. Patent No. 5,834,893 to Bulovic et al., which are incorporated herein by reference in their entirety.

[0590] Unless otherwise specified, any of the layers in the various embodiments may be deposited by any suitable method. For organic layers, preferred methods include thermal evaporation, inkjet printing (as described in U.S. Patent Nos. 6,013,982 and 6,087,196, which are incorporated herein by reference in their entirety), organic vapor deposition (OVPD) (as described in U.S. Patent No. 6,337,102 by Forrest et al., which are incorporated herein by reference in their entirety), and deposition via organic vapor jet printing (OVJP, also known as organic vapor jet deposition (OVJD)) (as described in U.S. Patent No. 7,431,968, which is incorporated herein by reference in its entirety). Other suitable deposition methods include spin coating and other solution-based processes. Solution-based processes are preferably performed in a nitrogen or inert atmosphere. For other layers, preferred methods include thermal evaporation, sputtering, chemical vapor deposition, atomic layer deposition, and electron beam deposition. Preferred patterning methods include patterning via mask deposition, photolithography, and cold soldering (as described in U.S. Patents 6,294,398 and 6,468,819, which are incorporated herein by reference in their entirety) and some of the methods associated with deposition methods such as inkjet and organic vapor jet printing (OVJP). Other methods may also be used. The material to be deposited may be modified to suit a particular deposition method. For example, branched or unbranched substituents, preferably containing at least three carbons, such as alkyl and aryl groups, may be used in small molecules to enhance their solution handling ability. Substituents having 20 or more carbons may be used, with 3 to 20 carbons being a preferred range. Materials with asymmetric structures may have better solution handling ability than materials with symmetric structures because asymmetric materials may have a lower tendency to recrystallize. Dendritic polymer substituents may be used to enhance the solution handling ability of small molecules.

[0591] The device manufactured according to embodiments of this disclosure may optionally further include a barrier layer. One use of the barrier layer is to protect the electrodes and organic layers from damage caused by exposure to harmful substances in an environment including moisture, vapors, and / or gases. The barrier layer may be deposited above, below, or adjacent to a substrate or electrode, or above any other part of the device, including edges. The barrier layer may comprise a single layer or multiple layers. The barrier layer can be formed using various known chemical vapor deposition techniques and may comprise compositions having a single phase and compositions having multiple phases. Any suitable material or combination of materials may be used for the barrier layer. Inorganic or organic compounds, or both, may be incorporated into the barrier layer. Preferred barrier layers comprise multiple alternative layers of materials including: polymeric and nonpolymeric materials; organic and inorganic materials; or mixtures of polymeric and nonpolymeric materials, an example of which is described in U.S. Patent No. 7,968,146, PCT Patent Application Nos. PCT / US2007 / 023098 and PCT / US2009 / 042829, which are incorporated herein by reference in their entirety.

[0592] The apparatus manufactured according to embodiments of this disclosure can be incorporated into a wide variety of electronic component modules (or units), which can be incorporated into a variety of electronic products or intermediate components. Examples of such electronic products or intermediate components include displays, lighting devices (such as discrete light source devices or lighting panels), etc., which can be utilized by end-user product manufacturers. The electronic component module may optionally include driving electronics and / or a power supply. The apparatus manufactured according to embodiments of this disclosure can be incorporated into a wide variety of consumer products having one or more electronic component modules (or units) incorporated therein. A consumer product incorporating an OLED is disclosed, wherein the OLED includes compounds of this disclosure in its organic layer. The consumer product should include any type of product containing one or more light sources and / or one or more of some type of visual display. Examples of the consumer products described include flat panel displays, curved displays, computer monitors, medical monitors, televisions, billboards, lights for internal or external lighting and / or signaling, head-up displays, fully transparent or partially transparent displays, flexible displays, rollable displays, foldable displays, stretchable displays, laser printers, telephones, cellular phones, tablet computers, phablets, personal digital assistants (PDAs), wearable devices, laptop computers, digital cameras, camcorders, viewfinders, microdisplays (displays with a diagonal of less than 2 inches), 3D displays, virtual reality or augmented reality displays, vehicles, video walls comprising multiple tiled displays, theater or stadium screens, phototherapy devices, and signage. Various control mechanisms, including passive and active matrices, can be used to control the devices manufactured according to this disclosure. Many of the devices are intended for use in temperature ranges comfortable for humans, such as 18°C ​​to 30°C, and more preferably at room temperature (20-25°C), but can be used outside this temperature range (e.g., -40°C to +80°C).

[0593] Further details regarding OLEDs and the definitions described above can be found in U.S. Patent No. 7,279,704, which is incorporated herein by reference in its entirety.

[0594] The materials and structures described herein can be applied to devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors can utilize the materials and structures described. More generally, organic devices such as organic transistors can utilize the materials and structures described.

[0595] In some embodiments, the OLED has one or more features selected from the group consisting of: flexible, rollable, foldable, stretchable, and bendable. In some embodiments, the OLED is transparent or translucent. In some embodiments, the OLED further comprises a layer including carbon nanotubes. In some embodiments, the OLED further comprises one or more quantum dots. Such quantum dots may be in the emission layer or in other functional layers, such as conversion layers.

[0596] In some embodiments, the OLED comprises an RGB pixel arrangement or a white pixel arrangement with a color filter. In some embodiments, the OLED is a mobile device, a handheld device, or a wearable device. In some embodiments, the OLED is a display panel with a diagonal of less than 10 inches or an area of ​​less than 50 square inches. In some embodiments, the OLED is a display panel with a diagonal of at least 10 inches or an area of ​​at least 50 square inches. In some embodiments, the OLED is a lighting panel.

[0597] D. Other materials used in OLEDs

[0598] The materials described herein are various examples of materials that can be used in specific layers in OLEDs. They can also be used in combination with a wide variety of other materials present in the device. For example, the emission dopants disclosed herein can be used by the emission dopants themselves in the EML, or in combination with a wide variety of other emitters, hosts, transport layers, barrier layers, implantation layers, electrodes, and other layers that may be present. The materials described or mentioned below are non-limiting examples of materials that can be used in combination with the compounds and devices disclosed herein, and those skilled in the art can readily consult the literature to identify other materials that can be used in combination.

[0599] a) Conductive dopants:

[0600] Charge transport layers can be doped with conductive dopants to substantially alter their charge carrier density, which in turn changes their conductivity. Conductivity can be increased by generating charge carriers in the matrix material, and, depending on the type of dopant, variations in the Fermi level of the semiconductor can also be achieved. Hole transport layers can be doped with p-type conductive dopants, and n-type conductive dopants are used in electron transport layers. In some embodiments, the conductive dopant comprises at least one chemical moiety selected from the group consisting of: cyano, fluorinated aryl or heteroaryl, fluorinated alkyl or cycloalkyl, alkylene, heteroaryl, amide, benzodithiophene, and highly conjugated heteroaryl groups extended by acyclic double bonds.

[0601] b) HIL / HTL:

[0602] The hole injection / transport materials used in this disclosure are not particularly limited, and any compound may be used, provided that the compound is commonly used as a hole injection / transport material. Examples of materials include (but are not limited to): phthalocyanine or porphyrin derivatives; aromatic amine derivatives; indole-carbazole derivatives; polymers containing fluorinated hydrocarbons; polymers with conductive dopants; conductive polymers, such as PEDOT / PSS; self-assembled monomers derived from compounds such as phosphonic acids and silane derivatives; and metal oxide derivatives, such as MoO. x p-type semiconductive organic compounds, such as 1,4,5,8,9,12-hexaazatriphenylhexacarbonitrile; metal complexes; and crosslinkable compounds.

[0603] Examples of aromatic amine derivatives used for HIL or HTL include (but are not limited to) the following general structures: , , , ,and .

[0604] Ar 1 To Ar 9 Each of these is selected from: the group consisting of, for example, aromatic cyclic compounds such as: benzene, biphenyl, biphenylene, triphenylene, naphthalene, anthracene, phenanthrene, fluorene, pyrene, β-carbamate, perylene, and azulene; and the group consisting of, for example, aromatic heterocyclic compounds such as: dibenzothiophene, dibenzofuran, dibenzoselenene, furan, thiophene, benzofuran, benzothiophene, benzoselenene, carbazole, indolocarbazole, pyridinylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxtriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxthiazine, oxadiazine, indole, benzimidazole, indazole, inoxazine, benzene The group consisting of benzoxazole, benzoisoxazole, benzothiazole, quinoline, isoquinoline, cinnamoline, quinazoline, quinoxaline, naphthidine, phthalazine, pteridine, oxanthracene, acridine, phenazine, phenothiazine, phenoxazine, benzofuranopyridine, furanopyridine, benzothiophenopyridine, thiophenopyridine, benzoselenopyridine, and selelenopyridine; and the group consisting of 2 to 10 cyclic structural units, said cyclic structural units being groups of the same or different types selected from aromatic hydrocarbon cyclic groups and aromatic heterocyclic groups and bonded to each other directly or via at least one of oxygen, nitrogen, sulfur, silicon, phosphorus, boron, chain structural units, and aliphatic cyclic groups. 1 To Ar 9 Each of them may be unsubstituted or may be substituted with the general substituents described above, and any two substituents may be joined or fused into a ring.

[0605] In some embodiments, each Ar 1 To Ar 9Independently includes portions selected from the following groups:

[0606] , , , , , , and ;

[0607] Where k is an integer from 1 to 20; X 101 To X 108 It is C or N; Z 101 It is C, N, O, or S.

[0608] Examples of metal complexes used in HIL or HTL include, but are not limited to, the following general formula:

[0609] Met is a metal with an atomic weight greater than 40; (Y 101 -Y 102 ) is a bidentate ligand, Y 101 and Y 102 The coordinating atoms are independently selected from C, N, O, P, and S; L 101 It is another ligand; k' is an integer value from 1 to the maximum number of ligands that can be bound to the metal; and k'+k" is the maximum number of ligands that can be bound to the metal.

[0610] In some embodiments, (Y) 101 -Y 102 (Y) is a 2-phenylpyridine or 2-phenylimidazole derivative. In some embodiments, (Y) 101 -Y 102 Met is a carbene ligand. In some embodiments, Met is selected from Ir, Pt, Pd, Os, Cu, and Zn. In some embodiments, the metal complex has a relative... + The minimum oxidation potential in solution with / Fc coupling is less than about 0.6 V.

[0611] In some embodiments, the HIL / HTL material is selected from the group consisting of: phthalocyanine and porphyrin compounds, starburst triarylamine, CF xFluorinated hydrocarbon polymers, conductive polymers (e.g., PEDOT:PSS, polyaniline, polythiophene), phosphonic acids and silane SAMs, triarylamines or polythiophene polymers containing conductive dopants, organic compounds containing conductive inorganic compounds (such as molybdenum oxide and tungsten oxide), n-type semiconductive organic complexes, organometallic complexes, crosslinkable compounds, polythiophene-based polymers and copolymers, triarylamines, triarylamines containing spirofluorene cores, arylamine carbazole compounds, triarylamines containing (di)benzothiophene / (di)benzofuran, indole-carbazole, isoindole compounds, and metal carbene complexes.

[0612] c) EBL:

[0613] An electron blocking layer (EBL) can be used to reduce the number of electrons and / or excitons leaving the emitter layer. The presence of such a blocking layer in a device can result in generally higher efficiency and / or longer lifetime compared to similar devices lacking a blocking layer. Furthermore, the blocking layer can be used to confine emission to a desired area of ​​the OLED. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and / or a higher triplet energy compared to one or more emitters closest to the EBL interface. In some embodiments, the compound used in the EBL contains at least one carbazole group and / or at least one arylamine group. In some embodiments, the HOMO level of the compound used in the EBL is shallower than the HOMO level of one or more of the bodies in the EML. In some embodiments, the compound used in the EBL contains the same molecule or the same functional groups as those used in one of the bodies described below.

[0614] d) Main body:

[0615] The light-emitting layer of the organic EL device disclosed herein preferably contains at least a light-emitting material as a dopant and a host material. Examples of the host material are not particularly limited, and any metal complex or organic compound can be used, as long as the host does not completely quench the emission of the dopant.

[0616] Examples of metal complexes used as the host preferably have the following general formula:

[0617]

[0618] Where Met is a metal; (Y) 103 -Y 104 ) is a bidentate ligand, Y 103 and Y 104 The coordinating atoms are independently selected from C, N, O, P, and S; L 101 It is another ligand; k' is an integer value from 1 to the maximum number of ligands that can be bound to the metal; and k'+k" is the maximum number of ligands that can be bound to the metal.

[0619] In some embodiments, the metal complex is:

[0620]

[0621] (ON) is a bidentate ligand of a metal that coordinates with O and N atoms.

[0622] In some embodiments, Met is selected from Ir and Pt. In another embodiment, (Y 103 -Y 104 ) is a carbaene ligand.

[0623] In some embodiments, the host compound contains at least one selected from the group consisting of, for example, aromatic hydrocarbon cyclic compounds such as: benzene, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenanthrene, fluorene, pyrene, β-carbamate, perylene, and azurite; and aromatic heterocyclic compounds such as: dibenzothiophene, dibenzofuran, dibenzoselenene, furan, thiophene, benzofuran, benzothiophene, benzoselenene, carbazole, indolocarbazole, pyridinylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, and oxazole. Thiazole, oxadiazole, oxtriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxthiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benziisoxazole, benzothiazazole, quinoline, isoquinoline, cinnamoline, quinazoline, quinoxaline, naphthidine, phthalazine, pteridine, oxanthracene, acridine, phenazine, phenothiazine, phenothiazine, azira-dibenzothiophene, azira-dibenzofuran, azira-dibenzoselenophene, azira-carbazole, azira-indole-carbazole, azira-triphenylene, azira-tetraphenylene, 5λ 2 -Benzo[d]benzo[4,5]imidazo[3,2-a]imidazolium, 5,9-dioxa-13b-boronazonaphtho[3,2,1-de]anthracene; and groups consisting of 2 to 10 cyclic structural units, said cyclic structural units being groups of the same or different types selected from aromatic hydrocarbon cyclic groups and aromatic heterocyclic groups and bonded to each other directly or via at least one of oxygen, nitrogen, sulfur, silicon, phosphorus, boron, chain structural units, and aliphatic cyclic groups. Each option within each group may be unsubstituted or may be substituted with general substituents as described herein or may be further fused.

[0624] In some embodiments, the host compound comprises at least one portion selected from the group consisting of:

[0625] , , , , , , , , , , , , , , , , , , , , and ,

[0626] Where k is an integer between 0 and 20 or between 1 and 20. X 101 To X 108 Independently selected from C or N. Z 101 and Z 102 It is independently selected from C, N, O, or S.

[0627] In some embodiments, the host material is selected from the group consisting of: arylcarbazole, metal 8-hydroxyquinoline compounds (e.g., alq3, balq), metal phenoxybenzothiazole compounds, conjugated oligomers and polymers (e.g., polyfluorene), aromatic fused rings, zinc complexes, alkyl-based compounds, aryltriphenylene compounds, polyfused heteroaryl compounds, donor-acceptor molecules, dibenzofuran / dibenzothiophene compounds, polymers (e.g., pvk), spirofluorene compounds, spirofluorene-carbazole Zrazole compounds, indolocarbazole, 5-membered electron-deficient heterocycles (e.g., triazoles, oxadiazoles), tetraphenylene complexes, metal phenoxypyridine compounds, metal coordination complexes (e.g., Zn, Al containing N^N ligands), dibenzothiophene / dibenzofuran-carbazole compounds, silicon / germanium aryl compounds, aryl benzoyl esters, non-conjugated carbazoles, aza-carbazole / dibenzofuran / dibenzothiophene compounds, and high triplet state organometallic complexes (e.g., metal-carbaene complexes).

[0628] e) Emitter material in EML:

[0629] One or more emitter materials may be used in conjunction with the compounds or devices disclosed herein. The emitter materials may be emittant or non-emittent in current devices as described herein. Examples of emitter materials are not particularly limited, and any compound may be used as long as it is capable of generating emission in a conventional OLED device. Examples of suitable emitter materials include, but are not limited to, compounds capable of generating emission via phosphorescence, non-delayed fluorescence, delayed fluorescence (especially thermally activated delayed fluorescence, i.e., TADF (also known as E-type delayed fluorescence)), triplet-triplet annihilation, or combinations thereof.

[0630] In some embodiments, the emitter material has the formula M(L)1 ) x (L 2 ) y (L 3 ) z ;

[0631] Where L 1 L 2 and L 3 They can be the same or different;

[0632] Where x is 1, 2, or 3;

[0633] Where y is 0, 1, or 2;

[0634] Where z is 0, 1, or 2;

[0635] Where x+y+z is the oxidation state of the metal M;

[0636] Where L 1 Select the group consisting of structures from the following list of ligands:

[0637] , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , and ;

[0638] Each L 2 and L 3 Independent freedom of choice The group consisting of structures in the ligand list; where:

[0639] M is selected from the following groups: Ir, Rh, Re, Ru, Os, Pt, Pd, Zn, Au, Ag, and Cu;

[0640] T can be freely selected from the following groups: B, Al, Ga, and In;

[0641] K 1' It is a direct key or a selection of the following groups: NR e PR e , O, S and Se;

[0642] Each Y 1 To Y 15 Independently select groups composed of free carbon and nitrogen;

[0643] Y' selects from the following groups: BR e NR e PR e ,O,S,Se,C=O,S=O,SO2,CR e R f SiR e R f and GeR e R f ;

[0644] Each R a R b R c and R d It can independently represent monosubstituted to the maximum possible number of substitutions or no substitution;

[0645] Each R a1 R b1 R c1 R d1 R a R b R c R d R e and R f Independently, it is hydrogen or a substituent selected from the group of universal substituents as defined herein; and

[0646] Any two substituents can fused or joined to form a ring or a polydentate ligand.

[0647] In some embodiments, the emitter material is selected from the group consisting of the following dopant group 1:

[0648] , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , and ,

[0649] in

[0650] X 96 To X 99 Each of them is independently C or N;

[0651] Each Y 100 Independently select the groups composed of NR", O", S and Se;

[0652] R 10a R 20a R 30a R 40a and R 50a Each of these terms independently represents monosubstituted, at most maximum substituted, or unsubstituted.

[0653] R, R', R", R 10a R 11a R 12a R 13a R 20a R 30a R 40a R50a R 60 R 70 R 97 R 98 and R 99 Each of them is independently hydrogen or a substituent selected from the group of general substituents as defined herein; any two substituents may join or fuse to form a ring.

[0654] In some embodiments, the emitter material is selected from the group consisting of the following dopant group 2:

[0655] , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , and ,

[0656] in:

[0657] Each Y 100 Independently select the groups composed of NR", O", S and Se;

[0658] L is independently selected from the following groups: direct bond, BR", BR"R"', NR", PR", O, S, Se, C=O, C=S, C=Se, C=NR", C=CR"R"', S=O, SO2, CR", CR"R"', SiR"R"', GeR"R"', alkyl, cycloalkyl, aryl, heteroaryl and combinations thereof;

[0659] X 100 and X 200 Each time it appears, select from the following groups: O, S, Se, NR" and CR"R"';

[0660] Each R A" R B" R C" R D" R E" and R F" Independently represent monosubstituted, at most maximum substituted, or unsubstituted;

[0661] R, R', R", R"', R A1' R A2' R A" R B" R C" RD" R E" R F" R G" R H" R I" R J" R K" R L" R M" and R N" Each of them is independently hydrogen or a substituent selected from the group of general substituents as defined herein; and any two substituents may join or fuse to form a ring.

[0662] In some embodiments of dopant groups 1 and 2 above, each unsubstituted aromatic carbon atom may be replaced by N to form a nitrogen heterocycle. In some embodiments, the maximum number of N atoms in a ring is 1 or 2. In some embodiments of dopant group 2 above, each Pt atom in the formula may be replaced by a Pd atom.

[0663] In some embodiments of OLEDs, the delayed fluorescence material comprises at least one donor group and at least one acceptor group. In some embodiments, the delayed fluorescence material is a metal complex. In some embodiments, the delayed fluorescence material is a non-metallic complex. In some embodiments, the delayed fluorescence material is a Zn, Cu, Ag, or Au complex.

[0664] In some embodiments of OLEDs, the delayed fluorescence material has the formula M(L 5 (L) 6 ), where M is Cu, Ag, or Au, L 5 and L 6 Different, and L 5 and L 6 Choose independently from the following groups:

[0665] , , , ¸ , , , , , , , , , , , , , , , , , , , , , and ;

[0666] Where A 1 - A 9 Each is independently selected from C or N;

[0667] Each R P R Q and R U Independently represent monosubstituted, at most maximum substituted, or unsubstituted;

[0668] Each R P R P R U R SA R SB R RA R RB R RC R RD R RE and R RF Substituents are independently hydrogen or selected from the group of general substituents as defined herein; any two substituents may join or fuse to form a ring.

[0669] In some embodiments of the OLED, the delayed fluorescence material comprises at least one donor portion selected from the group consisting of:

[0670] , , , , , , , , , , , , , , , , , , , ,and ;

[0671] Where Y T Y U Y V and Y W Each of the following groups is selected independently: B, C, Si, Ge, N, P, O, S, Se, C=O, S=O, and SO2.

[0672] In some of the above embodiments, any carbon ring atom in each benzene ring of any of the above structures, up to a total of up to three carbon ring atoms, together with their substituents, may be replaced by N.

[0673] In some embodiments, the delayed fluorescence material comprises at least one acceptor moiety selected from the group consisting of: nitrile, isonitrile, borane, fluoride, pyridine, pyrimidine, pyrazine, triazine, aza-carbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, aza-triphenylene, imidazole, pyrazole, oxazole, thiazole, isoxazole, isothiazole, triazole, thiadiazole, and oxadiazole. In some embodiments, the acceptor moiety and donor moiety as described herein may be directly linked via a conjugated linker group or a non-conjugated linker group (such as sp...). 3 (Carbon or silicon atoms) are linked together.

[0674] In some embodiments, the fluorescent material comprises at least one chemical moiety selected from the group consisting of:

[0675] , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , and ;

[0676] Where Y F Y G Y H and Y I Each of the following groups is selected independently: B, C, Si, Ge, N, P, O, S, Se, C=O, S=O, and SO2;

[0677] Where X F and X G Each group is independently selected from the groups composed of C and N.

[0678] In some of the above embodiments, any carbon ring atom in each benzene ring of any of the above structures, up to a total of up to three carbon ring atoms, together with their substituents, may be replaced by N.

[0679] f) HBL:

[0680] Hole blocking layers (HBLs) can be used to reduce the number of holes and / or excitons leaving the emitter layer. The presence of such blocking layers in a device can result in generally higher efficiency and / or longer lifetime compared to similar devices lacking a blocking layer. Furthermore, blocking layers can be used to confine emission to the desired area of ​​the OLED. In some embodiments, the HBL material has a lower HOMO (farthest from vacuum level) and / or higher triplet energy compared to one or more emitters closest to the HBL interface.

[0681] In some embodiments, the compounds used in HBL contain the same molecules or the same functional groups as those used in the main body described above.

[0682] In some embodiments, the compound used in HBL comprises at least one of the following portions selected from the group consisting of:

[0683] , , , , , and Where k is an integer from 1 to 20; L 101 It is another ligand, and k' is an integer from 1 to 3.

[0684] g) ETL:

[0685] An electron transport layer (ETL) may comprise a material capable of transporting electrons. The ETL may be intrinsic (undoped) or doped. Doping can be used to enhance conductivity. Examples of ETL materials are not particularly limited, and any metal complex or organic compound may be used, provided it is typically used for electron transport.

[0686] In some embodiments, the compounds used in the ETL contain at least one of the following portions in their molecules:

[0687] , , , , , , , . , and fullerenes; where k is an integer from 1 to 20, X 101 To X 108 Selected from C or N; Z 101 Choose a group consisting of C, N, O, and S.

[0688] In some embodiments, the metal complexes used in the ETL contain, but are not limited to, the following general formula:

[0689]

[0690] Wherein (ON) or (NN) are bidentate ligands of metals that coordinate with atoms O, N, or N,N; L 101 It is another ligand; k' is an integer value from 1 to the maximum number of ligands that can be bonded to the metal.

[0691] In some embodiments, the ETL material is selected from the group consisting of: anthracene-benzimidazole compounds, azirtriene derivatives, anthracene-benzothiazole compounds, metal 8-hydroxyquinoline compounds, metal hydroxybenzoquinoline compounds, bathocuprine compounds, 5-membered electron-deficient heterocycles (e.g., triazoles, oxadiazoles, imidazoles, benzimidazoles), thiophene compounds, arylborane compounds, fluorinated aromatic compounds, fullerenes (e.g., C60), triazine complexes, and Zn(N^N) complexes.

[0692] h) Charge Generation Layer (CGL)

[0693] In tandem or stacked OLEDs, the conduction layer (CGL) plays a fundamental role in performance. It consists of an n-doped layer and a p-doped layer, respectively, for injecting electrons and holes. Electrons and holes are supplied by the CGL and the electrodes. Electrons and holes consumed in the CGL are refilled by electrons and holes injected from the cathode and anode, respectively; subsequently, the bipolar current gradually reaches a steady state. Typical CGL materials contain n- and p-conductive dopants used in the transport layer.

[0694] In any of the compounds disclosed herein, hydrogen atoms may be partially or fully deuterated. The minimum amount of deuterated hydrogen in a compound is selected from the group consisting of: 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 99%, and 100%. As used herein, the percentage of deuteration has its general meaning and includes the percentage of all possible hydrogen and deuterium atoms replaced by deuterium atoms. In some embodiments, the deuterium atom is attached to an aromatic ring. In some embodiments, the deuterium atom is attached to a saturated carbon atom, such as an alkyl or cycloalkyl carbon atom. In some other embodiments, the deuterium atom is attached to a heteroatom, such as a Si or Ge atom.

[0695] It should be understood that the various embodiments described herein are merely examples and are not intended to limit the scope of the invention. For instance, many of the materials and structures described herein can be substituted with other materials and structures without departing from the spirit of the invention. The claimed invention may therefore include variations of the specific examples and preferred embodiments described herein, as will be apparent to those skilled in the art. It should be understood that various theories regarding why the invention works are not intended to be limiting.

[0696] E. Experimental Data

[0697] a) Preparation of example compounds

[0698]

[0699] (3,5-Diisopropyl-[1,1'-biphenyl]-4-yl)boric acid (36.2 g, 95% wt, 122 mmol) was dissolved in MeCN (550 mL) under nitrogen atmosphere and heated to 45 °C in a top-stirred three-necked flask. A solution of potassium fluoride (31.2 g, 536 mmol) in water (50 mL) was added, followed by a suspension of (+)-tartaric acid (40.2 g, 268 mmol) in THF (175 mL). The mixture was stirred at 45 °C for 2.5 h, cooled to room temperature, and the solvent was decanted. The solids were resuspended in MeCN (3 × 750 mL) and filtered. The combined filtrates were concentrated. The residue was redissolved in MeCN (550 mL) under nitrogen atmosphere and heated to 45 °C in a top-stirred three-necked flask.) A solution of potassium fluoride (31.2 g, 536 mmol) in water (50 mL) was added, followed by a suspension of (+)-tartaric acid (40.2 g, 268 mmol) in THF (175 mL). The mixture was stirred at 45 °C for 2 hours, cooled to room temperature, and the solvent was decanted. The solid was suspended in MeCN (3 × 750 mL) and filtered. The combined filtrates were concentrated under vacuum. The resulting solid was suspended in a mixture of hexane: methyl tert-butyl ether (MTBE) (1:1, 400 mL), sonicated for 5 minutes, and then stirred at room temperature for 30 minutes. The resulting thick suspension was filtered, the solid was washed with hexane: MTBE (1:1, 2 × 200 mL), and dried under vacuum to give potassium (3,5-diisopropyl-[1,1'-biphenyl]-4-yl)trifluoroborate (26.1 g, 74 mmol, 60%, 97% purity) as a colorless solid.

[0700]

[0701] A solution of KF (0.513 g, 8.83 mmol) in water (0.84 mL) was added to a mixture of (3,3′′,5,5′′-tetratert-butyl-[1,1′:3′,1′′-terphenyl]-2′-yl)boric acid (1.0 g, 2.0 mmol) in acetonitrile (8.4 mL). The resulting mixture was stirred at room temperature for 10 minutes to obtain a suspension of colorless solids. Additional acetonitrile (3 mL) was added, and the mixture was heated to 45 °C until homogeneous. A solution of tartaric acid in THF (4.2 mL) was added, and stirring was continued at the same temperature for 45 minutes. The mixture was cooled to room temperature, filtered, and washed with excess acetonitrile. The filtrate was concentrated to obtain a colorless solid, which was suspended in hexane and stirred at room temperature for 1 hour. The solid was then collected by vacuum filtration to obtain 0.76 g (67% yield) of potassium trifluoro(3,3′′,5,5′′-tetratert-butyl-[1,1′:3′,1′′-terphenyl]-2′-yl)-l4-borane in the form of a colorless solid.

[0702]

[0703] In a 2 L round-bottom flask, sodium tert-butoxide (23.8 g, 247 mmol) was added to a mixture of 4-(tert-butyl)-1-chloro-2-nitrobenzene (48.0 g, 225 mmol), 4-(tert-butyl)aniline (36.9 g, 247 mmol), XPhos Pd G2 (9.51 g, 11.2 mmol), and XPhos (10.7 g, 22.5 mmol) in toluene (900 mL). The reaction mixture was stirred and heated under reflux for 16 hours. The mixture was cooled to room temperature and concentrated to 300 mL. The solution was diluted with EtOAc and water. The aqueous and organic layers were separated, and the aqueous layer was extracted with EtOAc (×3). The combined organic matter was dried over MgSO4, filtered, and concentrated to give 4-(tert-butyl)-N-(4-(tert-butyl)phenyl)-2-nitroaniline (44.0 g, 54% yield, 90% purity) in the form of a brown / black oil, which was used in the next step without further purification.

[0704]

[0705] Add 4-(tert-butyl)-N-(4-(tert-butyl)phenyl)-2-nitroaniline (44.0 g, 90% wt, 121 mmol), ammonium chloride (64.9 g, 1.21 mol), and zinc (20 mesh, 63.5 g, 971 mmol) to a round-bottom flask in a mixture of EtOH (540 mL) and water (270 mL). After incubation at 80 °C for 3 hours, the mixture was heat-filtered through celite. The filtered material was diluted with EtOAc, and 2 M HCl (aqueous solution) was added until the white solid inorganic matter dissolved. The two-phase mixture was further diluted with water. The individual layers were separated and the aqueous layer was extracted with EtOAc (×3). The combined organic matter was dried over MgSO4, filtered, and concentrated to obtain a pink oil. The pink oil was dissolved in 1,4-dioxane (1 L) by heating to 90 °C. HCl (17.7 g, 121 mL, 4.00 mol, 485 mmol) was added dropwise to 1,4-dioxane. The reaction mixture was cooled to room temperature. After 3 days, a black precipitate formed. The precipitate was filtered and washed with cold Et2O to give the product as a white solid. The filtrate was concentrated to remove all volatiles, and the resulting purple gel was prepared with cold Et2O to give more white solid. This process was repeated 3 more times. All white solids were combined and washed again with cold Et2O to give the hydrochloride of 4-(tert-butyl)-N1-(4-(tert-butyl)phenyl)phenyl-1,2-diamine as a white solid (34.3 g, 85% yield).

[0706]

[0707] NH3 (28 wt%, in H2O, 230 mL, 2.98 mmol) was added to a stirred mixture of glyoxal (40 wt% in H2O, 140 mL, 1.22 mol) and 4-bromo-2-fluorobenzaldehyde (60.0 g, 296 mmol) in EtOH (800 mL). The reaction mixture was stirred at 50 °C for 18 hours, cooled to room temperature, and concentrated under vacuum. The crude product was purified by silica gel column chromatography and combined again to give a brown solid. This solid was prepared in methyl tert-butyl ether (TBME, 300 mL), filtered, washed with TBME (3 × 100 mL), and dried under vacuum to give 2-(4-bromo-2-fluorophenyl)-1H-imidazolium (28.0 g, 39% yield) as a light brown powder.

[0708]

[0709] Diethylene glycol dimethyl ether (400 mL) and isopropyl magnesium chloride (2 M THF solution, 300 mL, 600 mmol) were placed in a nitrogen-purged three-necked round-bottom flask equipped with a top stirrer. The solution was cooled to 0 °C, and methylamine (2 M THF solution, 230 mL, 460 mmol) was added over 5 minutes, and the resulting mixture was stirred at 0 °C for 1 hour. A suspension of 2-(4-bromo-2-fluorophenyl)-1H-imidazole (28.0 g, 115 mmol) in diethylene glycol dimethyl ether (400 mL) was added over 5 minutes. The resulting mixture was heated to 110 °C and stirred for 1 hour. The mixture was cooled to room temperature, poured into a saturated NH4Cl aqueous solution (700 mL), and diluted with EtOAc (700 mL). The phases were separated, and the aqueous layer was extracted with EtOAc (3 × 400 mL). The combined organic extracts were dried over MgSO4, filtered, and concentrated under vacuum. The crude product was purified in two batches by silica gel column chromatography to obtain 5-bromo-2-(1H-imidazol-2-yl)-N-methylaniline (31.4 g, 86% yield, 80% purity [19 wt% diethylene glycol dimethyl ether]) as a grayish-white powder.

[0710]

[0711] NEt3 (60 mL, 430 mmol) was added to a mixture of 5-bromo-2-(1H-imidazol-2-yl)-N-methylaniline (34.5 g, 137 mmol) and CDI (45 g, 280 mmol) in DCM (800 mL). The resulting mixture was stirred at room temperature for 18 hours and then concentrated under vacuum. The crude product was suspended in EtOAc (400 mL), diluted with water (400 mL), and sonicated for 2 min. The resulting solid was collected by filtration, washed with water (2 × 100 mL), and dried under vacuum to give 8-bromo-6-methylimidazo[1,2-c]quinazolin-5(6H)-one (36.5 g, 94% yield) as a grayish-white powder.

[0712]

[0713] In a dry round-bottom flask, 8-bromo-6-methylimidazo[1,2-c]quinazolin-5(6H)-one (6.94 g, 24.95 mmol), sodium tert-butoxide (3.60 g, 37.4 mmol), and 9H-carbazole (12.52 g, 74.9 mmol) were suspended in xylene (125 mL) and placed under a nitrogen atmosphere. Then, allyl palladium chloride dimer (0.457 g, 1.248 mmol) and cBRIDP (0.220 g, 0.624 mmol) were added, and the reaction mixture was heated to 120 °C and stirred for 16 hours. The reaction mixture was then cooled to room temperature and filtered through diatomaceous earth. The diatomaceous earth was washed with THF (3 × 750 mL), and the solvent was removed under reduced pressure. The crude product was used for the next step.

[0714]

[0715] MeOH (249 mL) was added to a round-bottom flask containing crude 8-(9H-carbazol-9-yl)-6-methylimidazo[1,2-c]quinazolin-5(6H)-one (9.09 g, 24.94 mmol) from the previous step and KOH (14.00 g, 249 mmol), and the reaction mixture was heated under reflux for 16 hours. The crude mixture was cooled to room temperature and then filtered through diatomaceous earth. The diatomaceous earth was washed with THF (3 × 750 mL). The resulting filtrate was concentrated and purified by silica gel column chromatography to give 5-(9H-carbazol-9-yl)-2-(1H-imidazo-2-yl)-N-methylaniline (4.78 g, 56.6% yield) as a pink solid.

[0716]

[0717] 8-Bromo-6-methylimidazo[1,2-c]quinazolin-5(6H)-one (8 g, 27.3 mmol), K3PO4 (17.40 g, 82 mmol), and (2,6-diisopropylphenyl)boronic acid (11.32 g, 54.7 mmol) were suspended in xylene (400 ml) under N2. Bi-DIME (0.903 g, 2.73 mmol) and palladium(II) acetate (0.307 g, 1.366 mmol) were added, and the reaction mixture was heated to 110 °C for 16 hours. The reaction mixture was cooled to room temperature and diluted with EtOAc (1 L) and water (0.75 L). The phases were separated, and the aqueous phase was extracted with EtOAc (1 L). The combined organic matter was dried over Na2SO4, filtered, and concentrated under vacuum to give a brown oil. The brown oil was further purified by silica gel column chromatography to give 8-(2,6-diisopropylphenyl)-6-methylimidazo[1,2-c]quinazolin-5(6H)-one (8.75 g, 87% yield) in the form of a grayish-white solid.

[0718]

[0719] 8-(2,6-diisopropylphenyl)-6-methylimidazo[1,2-c]quinazolin-5(6H)-one (8.75 g, 23.85 mmol) was dissolved in THF (200 mL) and MeOH (115 mL) under nitrogen atmosphere. KOH (13.38 g, 239 mmol) was added, and the reaction mixture was heated to 60 °C for 21 hours. The reaction mixture was cooled to room temperature and then concentrated under vacuum. The residue was dissolved in EtOAc (400 mL) and water (400 mL). The aqueous layer was extracted with EtOAc (2 × 200 mL), and the combined organic extracts were washed with brine (150 mL), dried with Na2SO4, filtered, and concentrated under vacuum to give an orange-brown solid 4-(1H-imidazol-2-yl)-2′,6′-diisopropyl-N-methyl-[1,1′-biphenyl]-3-amine (7.90 g, 97% yield).

[0720]

[0721] A mixture of 8-bromo-6-methylimidazo[1,2-c]quinazolin-5(6H)-one (2.85 g, 9.99 mmol), potassium phosphate (6.36 g, 30.0 mmol), and (2,6-dimethylphenyl)boronic acid (2.25 g, 15.00 mmol) in xylene (160 mL) was placed under a nitrogen atmosphere. (XPhos)Pd G4 (430 mg, 0.500 mmol) was added, and the mixture was heated to 110 °C for 1 hour. The mixture was cooled to room temperature, filtered through diatomaceous earth, and washed with EtOAc (150 mL). The filtrate was diluted with water (100 mL), and the aqueous layer was extracted with EtOAc (3 × 50 mL). The combined organic extracts were washed with brine (150 mL), dried over MgSO4, filtered, and concentrated under vacuum. The crude product was prepared in MTBE (30 mL) and sonicated for 2 minutes, then filtered, washed with MTBE (2 × 30 mL) and vacuum dried to obtain 2.23 g, 73.6% yield, of 8-(2,6-dimethylphenyl)-6-methylimidazo[1,2-c]quinazolin-5(6H)-one in colorless solid form.

[0722]

[0723] KOH (9.81 g, 149 mmol) was added to a solution of 8-(2,6-dimethylphenyl)-6-methylimidazo[1,2-c]quinazolin-5(6H)-one (4.51 g, 14.87 mmol) in MeOH (30 mL) and THF (60 mL) under nitrogen atmosphere. The resulting mixture was stirred at 60 °C for 18 hours under N2 atmosphere. The mixture was cooled to room temperature, concentrated under vacuum, and the residue was dissolved in EtOAc (100 mL) and water (100 mL). The aqueous layer was extracted with EtOAc (3 × 50 mL), and the combined organic extracts were washed with brine (100 mL), dried with MgSO4, filtered, and concentrated under vacuum. The crude product was purified by silica gel column chromatography to obtain 3.78 g of 4-(1H-imidazol-2-yl)-N,2',6'-trimethyl-[1,1'-biphenyl]-3-amine in yellow solid form (91% yield).

[0724]

[0725] A mixture of 2-bromoaniline (25 g, 145 mmol), (2-fluorophenyl)boronic acid (21.4 g, 153 mmol), and K₂CO₃ (60 g, 434 mmol) in 1,4-dioxane (680 mL) and water (220 mL) was placed under a nitrogen atmosphere. Then, a (dppf)PdCl₂-CH₂Cl₂ adduct (5.90 g, 7.22 mmol) was added, and the resulting mixture was stirred at 80 °C for 19 hours. The mixture was cooled to room temperature, filtered through diatomaceous earth, and washed with EtOAc (2 × 100 mL). The filtrate was washed with H₂O (300 mL) and brine (150 mL), dried (Na₂SO₄), filtered, concentrated, and purified by silica gel column chromatography to give 2′-fluoro-[1,1′-biphenyl]-2-amine (22.6 g, 82% yield) as a light pink solid.

[0726]

[0727] A mixture of 1,3-dibromo-2-fluorobenzene (13.5 g, 53.2 mmol), 2'-fluoro-[1,1'-biphenyl]-2-amine (5 g, 26.7 mmol), and Cs₂CO₃ (17.4 g, 53.4 mmol) in toluene (80 mL) was placed under N₂, and then Pd₂(dba)₃ (1.22 g, 1.332 mmol) and 4,5-bis(diphenylphosphino)-9,9-dimethyloxanthracene (xantphos) (1.55 g, 2.68 mmol) were added. The mixture was stirred under reflux for 3 days, cooled to room temperature, diluted with DCM (80 mL), filtered through diatomaceous earth, and washed with DCM (80 mL). The filtrate was concentrated and the crude product was purified by silica gel column chromatography to obtain N-(3-bromo-2-fluorophenyl)-2′-fluoro-[1,1′-biphenyl]-2-amine in the form of a pale yellow oil (9.26 g, 90% yield).

[0728]

[0729] A mixture of N-(3-bromo-2-fluorophenyl)-2′-fluoro-[1,1′-biphenyl]-2-amine (9.26 g, 24.17 mmol) and K₂CO₃ (10.02 g, 72.5 mmol) in NMP (40 mL) was stirred at 170 °C for 22 h. The mixture was cooled to room temperature, diluted with water (120 mL), and extracted with EtOAc (3 × 80 mL). The combined organic phases were washed with water (80 mL) and brine (80 mL), dried (Na₂SO₄), filtered, concentrated, and purified by silica gel column chromatography to give 9-(3-bromo-2-fluorophenyl)-9H-carbazole (8.42 g, 94% yield) as a colorless solid.

[0730]

[0731] Over 5 minutes, n-butyllithium (1.6 M, in hexane; 24 mL, 38.4 mmol) was added to a solution of 1-((2-(trimethylsilyl)ethoxy)methyl)-1H-imidazolium (5.63 g, 28.4 mmol) in 100 mL of THF at -78 °C. The resulting mixture was stirred at -78 °C for 15 minutes, and then zinc chloride (1.9 M, in MeTHF; 20 mL, 38.0 mmol) was added. The cooling bath was removed, and the mixture was warmed to room temperature over 15 minutes. A mixture of PEPPSI-iPr (0.772 g, 1.136 mmol), 9-(3-bromo-2-fluorophenyl)-9H-carbazole (8.40 g, 22.72 mmol), and 1,4-dioxane (100 mL) was added, and the resulting mixture was stirred at 110 °C for 21 hours. It was then cooled to room temperature, quenched with a saturated aqueous solution of NH4Cl (100 mL), diluted with water (150 mL), and extracted with EtOAc (3 × 150 mL). The combined organic phases were dried (Na2SO4), filtered, concentrated, and purified by silica gel column chromatography to obtain 9-(2-fluoro-3-(1-((2-(trimethylsilyl)ethoxy)methyl)-1H-imidazol-2-yl)phenyl)-9H-carbazole in colorless solid form (10.1 g, 72.9% yield, 75% purity), which was used in the next step without further purification.

[0732]

[0733] A solution of 9-(2-fluoro-3-(1-((2-(trimethylsilyl)ethoxy)methyl)-1H-imidazol-2-yl)phenyl)-9H-carbazole (13.3 g, 21.51 mmol) in HCl (3 M, in MeOH; 250 mL, 750 mmol) was stirred at 50 °C for 4 days, cooled to room temperature, and concentrated at 40 °C. Water (100 mL) and DCM (100 mL) were added, the solid was collected by filtration and washed with water (20 mL) and DCM (20 mL) to obtain a gray solid. This solid was suspended in 2 M NaOH aqueous solution (200 mL) and 9:1 DCM:iPrOH (200 mL), and the mixture was stirred at room temperature for 1 hour until the solid was completely dissolved. The aqueous phase was further extracted with DCM (2 × 50 mL), the combined organic phases were washed with brine (50 mL), dried (Na2SO4), filtered and concentrated to give 9-(2-fluoro-3-(1H-imidazol-2-yl)phenyl)-9H-carbazole (4.30 g, 58.0% yield) in the form of a light gray solid.

[0734]

[0735] Methylamine (2M, in THF; 3.1 mL, 6.20 mmol) was added over 2 minutes to a solution of isopropyl magnesium chloride (2M, in THF; 3.8 mL, 7.60 mmol) in diethylene glycol dimethyl ether (8 mL) at 0 °C. The mixture was stirred at 0 °C for 1 hour, and then a solution of 9-(2-fluoro-3-(1H-imidazol-2-yl)phenyl)-9H-carbazole (0.5 g, 1.527 mmol) in diethylene glycol dimethyl ether (6 mL) was added over 2 minutes. The mixture was stirred at 110 °C for 20 hours, cooled to room temperature, and quenched with a saturated aqueous solution of NH4Cl (10 mL). The mixture was diluted with water (10 mL) and extracted with EtOAc (3 × 10 mL). The combined organic phases were dried (Na2SO4), filtered, and concentrated to give a pale orange solid. DCM (10 mL) was added, followed by isohexane (10 mL). The suspension was stirred at room temperature for 1 hour, the solid was collected by filtration, washed with 1:1 DCM:isohexane (10 mL), and dried to give 2-(9H-carbazole-9-yl)-6-(1H-imidazol-2-yl)-N-methylaniline in the form of a grayish-white solid (0.476 g, 92% yield).

[0736]

[0737] Ammonia (28 wt%, in H₂O, 100 mL, 1.29 mol) was added to a stirred mixture of glyoxal (40 wt%, in H₂O, 60 mL, 0.52 mol) and 3-bromo-2-fluorobenzaldehyde (25.0 g, 123 mmol) in EtOH (300 mL). The reaction mixture was stirred at 50 °C for 18 hours, cooled to room temperature, and concentrated under vacuum. Purification by silica gel column chromatography yielded a dark brown solid (18 g). This solid was prepared in TBME (70 mL), filtered, washed with TBME (20 mL), and dried under vacuum to give a pale yellow solid of 2-(3-bromo-2-fluorophenyl)-1H-imidazolium (10.9 g, 36% yield).

[0738]

[0739] A mixture of 2-(3-bromo-2-fluorophenyl)-1H-imidazole (8.0 g, 33 mmol), phenylboronic acid (6.1 g, 50 mmol), and Na₂CO₃ (11.6 g, 110 mmol) in 1,4-dioxane (200 mL) and water (40 mL) was placed under a nitrogen atmosphere. (XPhos)Pd G₄ (1.43 g, 1.66 mmol) was added, and the mixture was stirred at 90 °C for 67 h, cooled to room temperature, and diluted with water (300 mL). The mixture was extracted with EtOAc (3 × 150 mL), and the combined organic phases were washed with brine (100 mL), dried (Na₂SO₄), filtered, and concentrated. Purification by silica gel column chromatography yielded 2-(2-fluoro-[1,1'-biphenyl]-3-yl)-1H-imidazole (7.16 g, 83% yield) as a light brown solid.

[0740]

[0741] Aniline (11 mL, 120 mmol) was added over 5 minutes to a solution of isopropyl magnesium chloride (2 M, in THF, 76 mL, 150 mmol) in diethylene glycol dimethyl ether (100 mL) at 0 °C. The mixture was stirred at 0 °C for 1 hour, and then a solution of 2-(2-fluoro-[1,1′-biphenyl]-3-yl)-1H-imidazolium (7.91 g, 30.5 mmol) in diethylene glycol dimethyl ether (80 mL) was added over 2 minutes. The mixture was stirred at 120 °C for 21 hours, cooled to room temperature, and quenched with a saturated aqueous solution of NH4Cl (250 mL). The mixture was diluted with water (150 mL) and extracted with EtOAc (3 × 150 mL). The combined organic phases were dried (Na₂SO₄), filtered, and concentrated at 70 °C. The resulting light brown solid was purified by silica gel column chromatography and then prepared with 4:1 isohexane:EtOAc (200 mL) and left to stand overnight. The solid was collected by filtration, washed with 4:1 isohexane:EtOAc (50 mL), then with isohexane (50 mL), and dried to give a grayish-white solid of 3-(1H-imidazol-2-yl)-N-phenyl-[1,1'-biphenyl]-2-amine (7.25 g, 67% yield, 88% purity), which was used without further purification.

[0742]

[0743] A solution of isopropyl magnesium chloride (2M, in THF, 80 mL, 160 mmol) in diethylene glycol dimethyl ether (150 mL) was cooled to 0°C, and methylamine (2M, in THF, 65 mL, 130 mmol) was added over 5 minutes. The mixture was stirred at 0°C for 1 hour, and then a solution of 2-(3-bromo-2-fluorophenyl)-1H-imidazole (7.43 g, 30.8 mmol) in diethylene glycol dimethyl ether (120 mL) was added over 10 minutes. The resulting mixture was heated to 110°C and stirred for 2.5 hours, then cooled to room temperature. The mixture was poured into a saturated aqueous solution of NH4Cl (300 mL), diluted with EtOAc (300 mL), and sonicated for 2 minutes. The layers were separated, and the aqueous phase was extracted with EtOAc (3 × 150 mL). The combined organic extracts were washed with water (3 × 150 mL) and brine (200 mL), dried over MgSO4, filtered, and concentrated. The crude product was purified by silica gel column chromatography to give 2-bromo-6-(1H-imidazol-2-yl)-N-methylaniline as an orange oil (6.24 g, 72% yield, >90% purity [7 wt% solvent]).

[0744]

[0745] Triethylamine (7.7 mL, 55 mmol) was added to a mixture of 2-bromo-6-(1H-imidazol-2-yl)-N-methylaniline (90% by weight, 6.24 g, 22.3 mmol) and CDI (5.40 g, 33.3 mmol) in DCM (70 mL). The resulting mixture was stirred at room temperature for 3 days. The mixture was concentrated under vacuum, and the crude extract was ground with water (80 mL), filtered, washed with water (3 × 20 mL), and dried under vacuum to give an orange solid. The aqueous filtrate was extracted with DCM (3 × 50 mL), the combined organic extracts were washed with water (2 × 20 mL) and brine (50 mL), and then concentrated under vacuum. The extract was combined with the precipitated solid and purified by silica gel column chromatography to give 7-bromo-6-methylimidazo[1,2-c]quinazolin-5(6H)-one (6.03 g, 96% yield) as a yellow solid.

[0746]

[0747] A mixture of 7-bromo-6-methylimidazo[1,2-c]quinazolin-5(6H)-one (6.03 g, 21.3 mmol), phenylboronic acid (2.90 g, 23.8 mmol), and K₂CO₃ (9.00 g, 65.1 mmol) in 1,4-dioxane (150 mL) and water (30 mL) was placed under a nitrogen atmosphere. (dppf)PdCl₂ (dcm adduct, 870 mg, 1.06 mmol) was added, and the mixture was stirred at 80 °C under nitrogen for 48 hours. Phenylboronic acid (2.90 g, 23.78 mmol) and (dppf)PdCl₂ (dcm adduct, 870 mg, 1.06 mmol) were further added, and stirring was continued at 80 °C for 4 hours. The mixture was cooled to room temperature, filtered through diatomaceous earth, and washed with EtOAc (2 × 50 mL). The filtrate was diluted with water (150 mL), the layers were separated, and the aqueous layer was extracted with EtOAc (3 × 100 mL). The combined organic extracts were washed with brine (150 mL), dried over MgSO4, filtered, and concentrated. The crude product was purified by silica gel column chromatography to give 6-methyl-7-phenylimidazo[1,2-c]quinazolin-5(6H)-one (4.75 g, 75% yield) as a pale yellow solid.

[0748]

[0749] KOH (3.70 g, 56.1 mmol) was added to a solution of 6-methyl-7-phenylimidazo[1,2-c]quinazolin-5(6H)-one (3.31 g, 11.4 mmol) in MeOH (15 mL) and THF (30 mL) under N2 conditions. The mixture was stirred at 60 °C for 2 hours and then cooled to room temperature. The mixture was filtered and concentrated under vacuum. The residue was dissolved in EtOAc (100 mL) and water (100 mL) was added. The layers were separated and the aqueous layer was extracted with EtOAc (3 × 60 mL). The combined organic extracts were washed with brine (100 mL), dried over MgSO4, filtered, and concentrated. The product was purified by silica gel column chromatography to obtain an orange oil, which was then treated with 1:3 TBME / isohexane (10 mL), sonicated for 5 minutes, and concentrated to obtain 3-(1H-imidazol-2-yl)-N-methyl-[1,1'-biphenyl]-2-amine (2.55 g, 84% yield) in the form of a yellow-brown solid.

[0750]

[0751] 1-((2-(trimethylsilyl)ethoxy)methyl)-1H-imidazole (2.011 g, 10.14 mmol) was dissolved in THF (50 mL), and the resulting solution was cooled to -78 °C and n-butyllithium (2.5 M, in hexane, 4.06 mL, 10.14 mmol) was added. The mixture was stirred at this temperature for 15 min, and then a zinc(II) chloride solution (1.9 M, in 2Me-THF, 5.82 mL, 11.06 mmol) was added, and the cooling bath was removed to allow the reaction mixture to warm to room temperature while stirring. Separately, 4-(tert-butyl)-2-chlorophenyltrifluoromethanesulfonate (2.92 g, 9.22 mmol) was combined with (dppf)PdCl2 (dcm adduct, 0.376 g, 0.461 mmol), and this mixture was added to the zincate solution. Then 1,4-dioxane (50 mL) was added and the mixture was heated to active reflux to distill off THF. The solution was refluxed for 24 hours. It was then cooled to room temperature, quenched with a saturated aqueous NH4Cl solution, and then transferred to a separatory funnel using water and EtOAc. The organic and aqueous layers were separated, and the aqueous layer was then extracted with EtOAc (3×). The combined organic matter was then washed with brine, dried (MgSO4), filtered, concentrated, and the crude residue was purified by silica gel column chromatography to give 2.70 g (80% yield) of 2-(4-(tert-butyl)-2-chlorophenyl)-1-((2-(trimethylsilyl)ethoxy)methyl)-1H-imidazolium as a grayish-white solid.

[0752]

[0753] 2-(4-(tert-butyl)-2-chlorophenyl)-1-((2-(trimethylsilyl)ethoxy)methyl)-1H-imidazolium (2.7 g, 7.40 mmol) was dissolved in ethanol (50 mL), hydrochloric acid (aqueous solution, 5 M, 20 mL, 100 mmol) was added, and the mixture was stirred at 70 °C for 16 hours. The mixture was concentrated to dryness, and the resulting solid was then suspended in a saturated aqueous solution of Na₂CO₃ and extracted three times with EtOAc. The organic matter was washed with brine, dried (Na₂SO₄), filtered, and concentrated to give 1.29 g (74% yield) of 2-(4-(tert-butyl)-2-chlorophenyl)-1H-imidazolium as a grayish-white solid.

[0754]

[0755] Isopropylamine (0.816 mL, 9.97 mmol) and 2-(4-(tert-butyl)-2-chlorophenyl)-1H-imidazole (0.936 g, 3.99 mmol) were combined in diethylene glycol dimethyl ether (20 mL) under N2 and cooled to 0 °C. A THF solution of isopropyl magnesium chloride (5.98 mL, 11.96 mmol) was added, and the resulting suspension was warmed to room temperature. The mixture was then heated to 150 °C for 2 days. The mixture was cooled to room temperature, quenched with a saturated aqueous NH4Cl solution, further diluted with EtOAc and water, and transferred to a separatory funnel. The aqueous and organic layers were separated, the organic matter was washed with brine, dried (Na2SO4), filtered, concentrated, and purified by silica gel column chromatography to give 0.42 g (41% yield) of 5-(tert-butyl)-2-(1H-imidazol-2-yl)-N-isopropylaniline as a colorless solid.

[0756]

[0757] In a 250 mL round-bottom flask, (9H-carbazole-1-yl)boronic acid (2.110 g, 9.999 mmol), 2-bromo-1H-benzis[d]imidazole (2.364 g, 12.00 mmol), and potassium carbonate (4.145 g, 3.0 Eq, 30.00 mmol) were combined in a mixture of 1,4-dioxane (41.8 mL) and water (8.32 mL) and bubbled with N2 for 5 min. Tetra(triphenylphosphine)palladium(0) (577.7 mg, 499.9 μmol) was added, followed by bubbling for another 3 min. The reaction mixture was then heated to 90 °C for 16 h. The reaction mixture was cooled to room temperature and poured into water (100 mL). The aqueous layer was extracted with ethyl acetate (3 × 100 mL). The combined organic extracts were dried over sodium sulfate (10 g), filtered, and concentrated under reduced pressure. The crude residue was purified by silica gel column chromatography to obtain 2.14 g (76% yield) of 1-(1H-benzo[d]imidazol-2-yl)-9H-carbazole as a pale yellow solid.

[0758]

[0759] A mixture of 2-bromo-6-iodoaniline (66.1 g, 222 mmol), 3-fluoro-4-(4,4,5,5-tetramethyl-1,3,2-dioxoboronyl-2-yl)benzonitrile (57.6 g, 233 mmol), potassium carbonate (61.3 g, 444 mmol), and 1,1′-bis(diphenylphosphino)ferrocene palladium(II) dichloride (3.26 g, 4.44 mmol) in 1,4-dioxane (600 mL) and water (150 mL) was stirred at 90 °C for 45 min under N2 atmosphere. An additional 3-fluoro-4-(4,4,5,5-tetramethyl-1,3,2-dioxoboronyl-2-yl)benzonitrile (3.29 g, 13.3 mmol) was added, and the reaction mixture was stirred at 90 °C for another 30 min. The reaction mixture was cooled to room temperature, diluted with EtOAc (600 mL), washed with semi-saturated brine (2 × 400 mL), brine (400 mL), dried (Na₂SO₄), filtered, and concentrated under vacuum to provide a crude product in the form of an orange solid. The solid was prepared from MeOH, washed with pentane, and dried under vacuum to provide a first batch of product. The mother liquor was concentrated under vacuum and prepared from MeOH, then washed with pentane to provide a second batch of product. The mother liquor was concentrated under vacuum, purified with a silica gel stopper, eluted with pure DCM, and concentrated under vacuum to provide a crude third batch of product. The three batches were combined and dried under vacuum to provide a brownish-yellow solid of 4-(2-amino-3-bromo-phenyl)-3-fluorobenzonitrile (61.2 g, 210 mmol, 95% yield).

[0760]

[0761] Potassium tert-butoxide (47.2 g, 420 mmol) was added to a solution of 4-(2-amino-3-bromo-phenyl)-3-fluorobenzonitrile (61.2 g, 210 mmol) in anhydrous dimethyl sulfoxide (600 mL). The reaction mixture was placed under a nitrogen atmosphere and then heated to 70 °C with stirring for 30 min. The reaction mixture was cooled to room temperature, diluted with EtOAc (500 mL), cooled to 0 °C, poured into a separatory funnel, and washed with ice-cold semi-saturated NH4Cl aqueous solution (2.00 L). The organic matter was separated. The aqueous solution was back-extracted with EtOAc (2 × 500 mL), the combined organic extracts were washed with brine (1.00 L), dried (Na2SO4), filtered, and concentrated under vacuum to provide a crude product. The crude product was prepared from MeOH, washed with pentane, and dried under vacuum to provide a first batch of product. The mother liquor was concentrated, prepared from MeOH, washed with pentane, and dried under vacuum to provide a second batch of product. The two batches were combined and then vacuum dried to provide 8-bromo-9H-carbazole-2-carboxynitrile as a brownish-yellow solid (34.1 g, 126 mmol, 60% yield).

[0762]

[0763] Over 30 minutes, n-butyllithium (2.5 M, 90 mL, 224 mmol) was added dropwise to a cooled (-78 °C) solution of 8-bromo-9H-carbazole-2-carboxynitrile (25.3 g, 93.3 mmol) in anhydrous tetrahydrofuran (373 mL). The reaction mixture was stirred at -78 °C for 30 minutes, followed by the addition of N,N-dimethylformamide (14 mL, 187 mmol) over 10 minutes. The reaction mixture was stirred at -78 °C for 30 minutes, then quenched with a saturated aqueous solution of NH4Cl and warmed to 20 °C. The resulting mixture was partitioned between EtOAc (300 mL) and water (100 mL). The organic matter was separated and back-extracted from the aqueous solution using EtOAc (2 × 100 mL). The combined organic extracts were washed with brine, dried (Na2SO4), passed through a phase separator, and concentrated under vacuum to provide a crude product. The crude product was prepared twice from warm (50°C) methanol, the solid was washed with cold methanol, then washed with pentane and dried under vacuum. The resulting solid was prepared twice from warm (50°C) acetone, the solid was washed with cold acetone, then washed with pentane and dried under vacuum, thus providing a brownish-yellow solid form of 8-formyl-9H-carbazole-2-carboxynitrile (12.0 g, 54.5 mmol, 58% yield).

[0764]

[0765] A mixture of 8-formyl-9H-carbazole-2-carboxynitrile (12.0 g, 54.5 mmol), 1,2-phenylenediamine (6.07 g, 56.1 mmol), and sodium metabisulfite (25.89 g, 136 mmol) in N,N-dimethylformamide (136 mL) was heated to 130 °C for 1 hour under a nitrogen atmosphere. The reaction mixture was cooled to room temperature, poured into water (600 mL), and the resulting precipitate was collected by filtration. The residue was washed with water (3×), then with MeOH (2×), and then with pentane. The solid was collected and dried under vacuum to provide the crude product. The crude product was prepared twice from warm (50 °C) methanol, and the solid was washed with cold methanol, then with pentane and dried under vacuum. The resulting solid was prepared twice from warm (50°C) acetone, washed with cold acetone, then washed with pentane and dried under vacuum to provide 8-(1H-benzimidazol-2-yl)-9H-carbazole-2-carboxynitrile in the form of a pale yellow solid (13.3 g, 43.1 mmol, 79% yield).

[0766]

[0767] In a 1 L round-bottom flask, 20.00 g (75.45 mmol) of 3-bromo-2-fluorodibenzo[b,d]furan 825-4, 20.85 g (150.9 mmol) of potassium carbonate, and 2-chloro-6-(4,4,5,5-tetramethyl-1,3,2-dioxoborhexacyclopentan-2-yl)aniline (28.69 g (113.2 mmol)) were combined in 20.00 mL of 1,4-dioxane and 50.00 mL of water. The resulting solution was placed under N2, and then tetra(triphenylphosphine)palladium(0) (21.251 g (18.390 mmol)) was added. The reaction mixture was heated to 85 °C for 16 hours. The reaction mixture was cooled to room temperature and diluted with 200 mL of ethyl acetate and 200 mL of water. The organic and aqueous layers were separated, and the aqueous layer was then extracted with ethyl acetate (2 × 100 mL). The organic matter was combined, dried over Na2SO4, filtered, and concentrated to a crude residue, which was then purified by silica gel column chromatography to 2-chloro-6-(2-fluorodibenzo[b,d]furan-3-yl)aniline as a colorless solid (16.2 g, 68.9% yield).

[0768]

[0769] In a 500 mL round-bottom flask, 16.00 g (51.32 mmol) of 2-chloro-6-(2-fluorodibenzo[b,d]furan-3-yl)aniline in 200.00 mL of DMSO was placed under N2. NaH (3.695 g, 154.0 mmol) was added to the solution, and the reaction mixture was heated to 120 °C and stirred for 72 hours. After cooling to room temperature, 500 mL of dichloromethane and 500 mL of water were added, and the mixture was transferred to a separatory funnel. The organic and aqueous layers were separated, and the aqueous layer was extracted twice with 100 mL of dichloromethane. The combined organic layers were dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography to obtain 10-chloro-11H-benzofurano[3,2-b]carbazole as a colorless solid (11.4 g, 76.1% yield).

[0770]

[0771] In a 500 mL round-bottom flask, 10-chloro-11H-benzofurano[3,2-b]carbazole (6.000 g, 20.57 mmol), bis(pinacol)diboron (10.45 g, 41.13 mmol), and 2-(dicyclohexylphosphino)-2′,4′,6′-tris(isopropyl)biphenyl (XPhos 1.961 g, 4.113 mmol) were combined in 1,4-dioxane (100.00 mL), and the solution was placed under a nitrogen atmosphere. Pd2(dba)3 (941.7 mg, 1.028 mmol) was added, and the reaction mixture was heated to 80 °C for 16 hours. The reaction mixture was cooled to room temperature and diluted with ethyl acetate (200 mL) and water (200 mL). The aqueous and organic layers were separated, and the aqueous layer was extracted with ethyl acetate (2 × 50 mL). The organic compounds were combined, dried with anhydrous Na2SO4, filtered, concentrated, and purified by silica gel column chromatography to obtain 10-(4,5,5,5-tetramethyl-1,3,2-dioxoboronyl-2-yl)-11H-benzofurano[3,2-b]carbazole as a grayish-white solid (3.2 g, 41% yield).

[0772]

[0773] In a 20 mL scintillation bottle, 10-(4,4,5,5-tetramethyl-1,3,2-dioxoboronyl-2-yl)-11H-benzofurano[3,2-b]carbazole (199.6 mg, 96% wt, 500 μmol), 2-bromo-1H-benzo[d]imidazole (118.2 mg, 600.0 μmol), and cesium carbonate (488.7 mg, 1.500 mmol) were combined. The reaction mixture was placed under a nitrogen atmosphere, and (Xphos)Pd G3 (42.32 mg, 50.00 μmol) was added. The bottle was sealed, and the reaction mixture was heated to 90 °C for 16 hours. The reaction mixture was cooled to room temperature, and additional (Xphos)Pd G3 (42.32 mg, 25.00 μmol) was added. The bottle was resealed under a nitrogen atmosphere and heated at 90°C for 3 days. The reaction mixture was cooled to room temperature and diluted with water and EtOAc. The layers were separated, and the organic matter was dried with sodium sulfate, filtered, and concentrated to a crude yellow solid. The crude yellow solid was purified by silica gel column chromatography to give 10-(1H-benzo[d]imidazol-2-yl)-11H-benzofurano[3,2-b]carbazole (80 mg, 43% yield) in the form of a pale yellow solid.

[0774]

[0775] A solution of 2-bromo-3-fluorodibenzo[b,d]furan (16.9 g, 63.8 mmol) and sodium tert-butoxide (17.8 g, 185 mmol) in anhydrous toluene (200 mL) at 22 °C was placed under a nitrogen atmosphere. 2-Chloro-6-methoxyaniline (9.13 g, 58.0 mmol) was added, followed by palladium(II) acetate (650 mg, 2.90 mmol) and tri-tert-butylphosphonium tetrafluoroborate (1.68 g, 5.80 mmol). The reaction mixture was heated to 100 °C for 2 hours. The reaction mixture was cooled to room temperature, diluted with EtOAc (300 mL), and quenched with a saturated NH4Cl solution (400 mL). The resulting two-phase mixture was partitioned, and the aqueous layer was extracted with DCM (3 × 250 mL). The combined organic compounds were concentrated and the crude product mixture was purified by silica gel column chromatography to give N-(2-chloro-6-methoxyphenyl)-3-fluorodibenzo[b,d]furan-2-amine as a light brown solid (15.7 g, 77% yield).

[0776]

[0777] Under a nitrogen atmosphere, a solution of boron tribromide in dichloromethane (110 mL, 1.000 mol, 110 mmol) was added dropwise to a solution of N-(2-chloro-6-methoxyphenyl)-3-fluorodibenzo[b,d]furan-2-amine (15.7 g, 45.9 mmol) in anhydrous dichloromethane (450 mL) at -60 °C. The reaction mixture was warmed to 0 °C and stirred for 1 hour. Additional dichloromethane (150 mL) was added, and the reaction mixture was stirred at 0 °C for 1 hour. The reaction mixture was gradually warmed to 22 °C and stirred for 2 hours, then cooled to 0 °C and quenched with water (250 mL). The resulting organic layer was separated, and the aqueous layer was extracted with CH₂Cl₂ (3 × 250 mL). The combined organic layers were washed with saturated NH₄Cl solution (3 × 250 mL), dried over MgSO₄, and concentrated under vacuum. The crude product was purified by silica gel column chromatography to obtain 3-chloro-2-((3-fluorodibenzo[b,d]furan-2-yl)amino)phenol in colorless solid form (13.4 g, 85% yield).

[0778]

[0779] Potassium carbonate (8.50 g, 61.5 mmol) was added to a solution of 3-chloro-2-((3-fluorodibenzo[b,d]furan-2-yl)amino)phenol (13.4 g, 40.9 mmol) in anhydrous MeCN (650 mL) under N2 atmosphere and at 22 °C. The reaction mixture was heated to 80 °C and stirred for 3 hours. The reaction mixture was cooled to room temperature and quenched with water (1.0 L). The resulting solid was separated by filtration, washed with water (3 × 500 mL), and suspended in DCM (500 mL). The organic layer was washed with a saturated aqueous solution of NH4Cl (500 mL), dried with MgSO4, and concentrated under vacuum to give 11-chloro-12H-benzofuran[3,2-b]phenoxazine (11.9 g, 91% yield) as a gray solid.

[0780]

[0781] A flask containing 11-chloro-12H-benzofurano[3,2-b]phenoxazine (12.6 g, 40.9 mmol), bis(pinacol)diboron (B2pin2, 15.5 g, 61.0 mmol), (Sphos)Pd(crotyl)Cl (1.25 g, 2.06 mmol), and SPhos (850 mg, 2.07 mmol) was placed under a nitrogen atmosphere. A solution of potassium 2-ethylhexanoate (KEH) in 2-MeTHF (13.7 g, 150 mL, 0.500 mol, 75.0 mmol) and additional dry 2-MeTHF (20.0 mL) were added at 22 °C. The reaction mixture was heated to 80 °C for 2 hours, then cooled to room temperature, and MeOH (250 mL) was added dropwise with stirring. The solid obtained by filtration was washed with MeOH (3 × 100 mL) and dried under vacuum to give 11-(4,4,5,5-tetramethyl-1,3,2-dioxoboronyl-2-yl)-12H-benzofurano[3,2-b]phenoxazine (13.6 g, 80% yield) as a gray solid.

[0782]

[0783] In a 40 mL scintillation flask, 11-(4,4,5,5-tetramethyl-1,3,2-dioxoboronyl-2-yl)-12H-benzofurano[3,2-b]phenoxazine (226.9 mg, 88 wt%, 500.1 μmol), 2-bromo-1H-benzo[d]imidazole (118.3 mg, 600.1 μmol), potassium carbonate (207.3 mg, 1.500 mmol), and tetrabutylammonium bromide (16.12 mg, 50.01 μmol) were combined in a mixture of toluene (2.9 mL), ethanol (1.4 mL), and water (0.7 mL). The reaction mixture was placed under a nitrogen atmosphere, and then tetra(triphenylphosphine)palladium(0) (28.90 mg, 25.01 μmol) was added. The flask was sealed, and the reaction mixture was heated to 80 °C for 16 hours. The reaction mixture was cooled to room temperature and poured into water (50 mL). The aqueous layer was extracted with dichloromethane (2 × 40 mL) and ethyl acetate (2 × 40 mL). The combined organic layers were dried over sodium sulfate (5 g), filtered, and concentrated under reduced pressure. The crude mixture was then purified by silica gel column chromatography to give 11-(1H-benzo[d]imidazol-2-yl)-12H-benzofurano[3,2-b]phenoxazine as a yellow solid (88 mg, 45% yield).

[0784]

[0785] Under a nitrogen atmosphere, 3-bromo-2-iodopyridine (7.399 g, 26.06 mmol) and (9H-carbazole-1-yl)boronic acid (5.000 g, 23.69 mmol) were combined in 1,4-dioxane (70.00 mL). A solution of potassium carbonate (6.549 g, 47.39 mmol) in water (14.00 mL) was added, followed by tetrakis(triphenylphosphine)palladium(0) (1.369 g, 1.185 mmol). The reaction mixture was then heated to 100 °C for 16 hours. The mixture was cooled to room temperature, diluted with water, and the resulting solids were collected by filtration. These solids were then redissolved in EtOAc (50 mL), and the solution was separated into layers using hexane (100 mL). The resulting mixture was allowed to stand for 2 days to form a crystalline material. The crystalline material was collected by filtration and washed with heptane to obtain 3.0 g (39% yield) of 1-(3-bromopyridin-2-yl)-9H-carbazole in the form of a grayish-white solid.

[0786]

[0787] Add the following to a 40 mL oven-dried vial: 2-(dicyclohexylphosphino-2′,4′,6′-triisopropyl-1,1′-biphenyl)(2′-methylamino-1,1′-biphenyl-2-yl)palladium(II) ((XPhos)Pd G4), 1.599 g, 1.856 mmol; 2-(dicyclohexylphosphino)-2′,4′,6′-tri(isopropyl)biphenyl (2.655 g, 5.569 mmol); diboronic acid (4.993 g, 55.69 mmol); potassium acetate (5.466 g, 55.69 mmol); and 1-(3-bromopyridin-2-yl)-9H-carbazole (6.000 g, 18.56 mmol). EtOH (50.00 mL) was added via syringe, and the resulting mixture was heated to 80 °C for 16 hours. The mixture was then concentrated and purified by silica gel column chromatography to give 1.0 g (19% yield) of 8H-pyrido[3',2':3,4][1,2]azaborinino[5,6,1-jk]carbazole-8-ol as a yellow solid.

[0788]

[0789] 8H-pyrido[3',2':3,4][1,2]azaboraxhexano[5,6,1-jk]carbazole-8-ol (2.020 g, 7.479 mmol) was dissolved in ethyl acetate (25.00 mL), and then N,N-dimethylethanolamine (733.3 mg, 830 μL, 8.227 mmol) was added. The resulting solution was stirred at room temperature for 16 hours. The mixture was then concentrated to dryness, and the resulting solid was suspended in diethyl ether and collected by vacuum filtration to give 1.40 g (55% yield) of 3',3'-dimethyl-3'l4,8l4-spiro[pyrido[3',2':3,4][1,2]azaboraxhexano[5,6,1-jk]carbazole-8,2'-[1,3,2]oxazolaborane] as a yellow solid.

[0790]

[0791] THF (3,000 mL) was transferred into a 40 mL vial containing 4-iodo-3,5-diisopropyl-1,1'-biphenyl (80.07 mg, 219.8 μmol), and placed under a nitrogen atmosphere and cooled to 0 °C. Mg(O) (5.0 mg, 0.21 mmol) was then added, and the reaction mixture was warmed to room temperature and stirred for 6 hours. Aliquots for analysis showed no conversion of the iodide starting material; therefore, the reaction was further cooled to -78 °C, and n-butyllithium (2.5 M, 0.082 mL, 0.21 mmol) was added dropwise using a syringe. Five minutes later, the solid 3',3'-dimethyl-3'l4,8l4-spiro[pyrido[3',2':3,4][1,2]azaborazhexano[5,6,1-jk]carbazole-8,2'-[1,3,2]oxazolane] (50 mg, 0.15 mmol) was added all at once. The cooling bath was removed, and the reaction mixture was warmed to room temperature with stirring for 16 hours. The reaction was quenched by adding a saturated aqueous solution of NH4Cl, and then further diluted with water and ethyl acetate and transferred to a separatory funnel. The organic and aqueous layers were separated, and the aqueous solution was further extracted with ethyl acetate (twice). The combined organic matter was washed with brine, dried with Na2SO4, filtered, concentrated, and purified by silica gel column chromatography to obtain 15 mg (21% yield) of 8-(3,5-diisopropyl-[1,1'-biphenyl]-4-yl)-8-H-pyrido[3',2':3,4][1,2]azaboronehexane[5,6,1-jk]carbazole as a pale yellow solid.

[0792]

[0793] Under a nitrogen atmosphere, 1-(3-bromopyridin-2-yl)-9H-carbazole (50.00 mg, 154.7 μmol) was dissolved in 2.000 mL of THF in a reaction flask and cooled to -78 °C. Isopropyl magnesium chloride-lithium chloride complex (270.5 μL, 1.300 mol, 351.6 μmol) was added dropwise via syringe, followed by stirring at the same temperature for 30 min, and then the mixture was warmed to room temperature with stirring for 1 hour. Dichlorodiphenylsilane (44.37 μL, 211.0 μmol) was then added, and the mixture was heated to 60 °C for 16 h. The reaction was quenched by adding a saturated aqueous NH4Cl solution, followed by further dilution with water and ethyl acetate and transfer to a separatory funnel. The organic and aqueous layers were separated, and the aqueous solution was further extracted twice with ethyl acetate. The combined organic matter was washed with brine, dried with Na2SO4, filtered, concentrated, and purified by silica gel column chromatography to obtain 50 mg (84% yield) of 8,8-diphenyl-8H-pyrido[3',2':3,4][1,2]azasilino[5,6,1-jk]carbazole as a pale yellow solid.

[0794]

[0795] 1-(3-bromopyridin-2-yl)-9H-carbazole (250 mg, 774 μmol) was dissolved in THF (2.000 mL) in a reaction flask and cooled to -78 °C under N2 atmosphere. Butyllithium (2.5 M, in hexane, 0.647 mL, 1.68 mmol) was added dropwise via syringe, and stirring was continued at the same temperature for 30 min. Then, dichlorodiphenylgermanane (0.148 mL, 701.0 μmol) was added, and the mixture was heated to 60 °C for 16 h. The reaction was quenched by adding saturated NH4Cl aqueous solution, followed by further dilution with water and ethyl acetate, and transferred to a separatory funnel. The organic and aqueous layers were separated, and the aqueous layer was further extracted with ethyl acetate (twice). The combined organic matter was washed with brine, dried with Na2SO4, filtered, concentrated, and purified by silica gel column chromatography to obtain 20 mg (7.0% yield) of 8,8-diphenyl-8H-pyrido[3',2':3,4][1,2]azagermino[5,6,1-jk]carbazole as a pale yellow solid.

[0796]

[0797] Methyl 2-chloronicotinate (1.789 g, 10.43 mmol) and (9H-carbazole-1-yl)boronic acid (2.000 g, 9.477 mmol) were combined in 1,4-dioxane (30.000 mL) and placed under a nitrogen atmosphere. A solution of potassium carbonate (2.620 g, 18.95 mmol) in water (6.0000 mL) was added, followed by tetrakis(triphenylphosphine)palladium(0) (547.6 mg, 473.9 μmol). The reaction mixture was then heated to 100 °C for 16 hours. The mixture was then cooled to room temperature and transferred to a separatory funnel using EtOAc and water. The aqueous and organic layers were separated, and the aqueous layer was then extracted with EtOAc (3 × 50 mL). The combined organic matter was washed with brine (100 mL), dried with Na2SO4, filtered, concentrated, and purified by silica gel column chromatography to obtain 2.1 g (82% yield) of 8H-[1,6]naphthyridino[8,7,6-jk]carbazole-8-one as a grayish-white solid.

[0798]

[0799] Under a nitrogen atmosphere, 2-fluoro-6-methoxybenzaldehyde (10.00 g, 64.9 mmol), 3-bromophenyl-1,2-diamine (12.13 g, 64.9 mmol), sodium metabisulfite (30.83 g, 162 mmol), and N,N-dimethylformamide (250 mL) were charged into a 1 L three-necked round-bottom flask equipped with a reflux condenser. The reaction mixture was heated at 130 °C for 3 hours. The reaction mixture was cooled to room temperature, poured onto ice, and stirred for 15 minutes. The resulting beige precipitate was collected by filtration, washed twice with water, and then dried under reduced pressure. 4-Bromo-2-(2-fluoro-6-methoxy-phenyl)-1H-benzimidazole (18.13 g, 87.0% yield) was then obtained.

[0800]

[0801] To a 1 L round-bottom flask, add 4-bromo-2-(2-fluoro-6-methoxy-phenyl)-1H-benzimidazole (15.00 g, 46.7 mmol), PdCl2(dppf) (1.72 g, 2.34 mmol), 2-(3-(tert-butyl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxoborhexacyclopentan-2-yl)phenyl)-4-phenylpyridine (20.27 g, 49.0 mmol), and sodium carbonate (9.90 g, 93.4 mmol). Evacuate the flask and backfill with N2 three times, then add degassed 1,4-dioxane (300 mL) and water (75 mL). Heat the mixture to 100 °C and stir for 3 hours. Then cool the reaction mixture to room temperature and filter through a diatomaceous earth mat, washing with EtOAc. The filtrate was concentrated under vacuum and then diluted with EtOAc (200 mL) and water (200 mL). The aqueous and organic layers were separated, and the aqueous layer was extracted with EtOAc (3 × 100 mL). The combined organic matter was passed through a hydrophobic glass frit and then concentrated under vacuum to produce a crude brown solid. The crude brown solid was purified by silica gel column chromatography to give a colorless solid of 4-(3-(tert-butyl)-5-(4-phenylpyridin-2-yl)phenyl)-2-(2-fluoro-6-methoxyphenyl)-1H-benzo[d]imidazole (23.86 g, 92.9% yield).

[0802]

[0803] 4-(3-(tert-butyl)-5-(4-phenylpyridin-2-yl)phenyl)-2-(2-fluoro-6-methoxyphenyl)-1H-benzo[d]imidazole (23.86 g, 45.2 mmol) and pyridine hydrochloride (40.00 g, 346 mmol) were heated to 160 °C for 3 hours under a nitrogen atmosphere. The mixture was cooled to room temperature and diluted with EtOAc and saturated NaHCO3 aqueous solution. The organic layer was collected, washed with brine, passed through a hydrophobic glass frit, and then concentrated under vacuum to give a crude residue, which was purified by silica gel column chromatography to give 2-(4-(3-(tert-butyl)-5-(4-phenylpyridin-2-yl)phenyl)-1H-benzo[d]imidazole-2-yl)-3-fluorophenol (19.92 g, 85.6% yield) as a colorless solid.

[0804]

[0805] A mixture of isopropyl magnesium chloride (2.0 M, in THF) (39.0 mL, 77.9 mmol) in diethylene glycol dimethyl ether (40 mL) was cooled to 0 °C, and methylamine (39.0 mL, 77.9 mmol) was added. The resulting mixture was stirred at 0 °C for 1 hour, and then a solution of 2-(4-(3-(tert-butyl)-5-(4-phenylpyridin-2-yl)phenyl)-1H-benzo[d]imidazol-2-yl)-3-fluorophenol (8.00 g, 15.6 mmol) in diethylene glycol dimethyl ether (40 mL) was added. The reaction mixture was heated to 120 °C and stirred for 4 hours. The mixture was cooled to room temperature, quenched with a saturated aqueous NH4Cl solution, and diluted with EtOAc. The aqueous and organic layers were separated, and the aqueous layer was extracted with EtOAc (3 × 100 mL). The combined organic matter was washed with brine and passed through a hydrophobic glass frit. The filtrate was concentrated under vacuum to obtain a crude residue, which was then purified by silica gel column chromatography to give 2-(4-(3-(tert-butyl)-5-(4-phenylpyridin-2-yl)phenyl)-1H-benzo[d]imidazol-2-yl)-3-(methylamino)phenol (4.60 g, 56.3% yield) in the form of a dark green solid.

[0806]

[0807] Representative boron step 1. 1-(1H-benzo[d]imidazol-2-yl)-9H-carbazole (900.0 mg, 3.177 mmol), potassium trifluoroborate (3,5-diisopropyl-[1,1'-biphenyl]-4-yl) (1.640 g, 4.765 mmol), and lithium chloride (701.5 mg, 5.21 Eq, 16.55 mmol) were added to a 100 mL three-necked round-bottom container equipped with a stir bar. Anhydrous diethylene glycol dimethyl ether (30.00 mL) was added, and the reaction mixture was then placed under a nitrogen atmosphere. 2,3,4,6,7,8,9,10-octahydropyrimidino[1,2-a]acoxane (DBU, 1.451 g, 1.425 mL, 9.530 mmol) was added via syringe. The reaction mixture was heated to 150 °C and stirred for 3 hours. The reaction mixture was cooled to room temperature and concentrated under reduced pressure, then purified by silica gel column chromatography to give 1.18 g (70.0% yield) of 9-(3,5-diisopropyl-[1,1'-biphenyl]-4-yl)-9H-benzo[4',5']imidazo[1',2':3,4][1,3,2]diazaborinino[5,6,1-jk]carbazole as a pale yellow solid.

[0808] The ligands in Table 1 were synthesized using a representative boron step 1, and their corresponding diamine precursors were selected from the following list: [4-(1H-imidazol-2-yl)-N,2',6'-trimethyl-[1,1'-biphenyl]-3-amine, 4-(1H-imidazol-2-yl)-2',6'-diisopropyl-N-methyl-[1,1'-biphenyl]-3-amine, 5-(9H-carbazol-9-yl)-2 -(1H-imidazol-2-yl)-N-methylaniline, 2-(9H-carbazol-9-yl)-6-(1H-imidazol-2-yl)-N-methylaniline, 3-(1H-imidazol-2-yl)-N-methyl-[1,1'-biphenyl]-2-amine, 3-(1H-imidazol-2-yl)-N-phenyl-[1,1'-biphenyl]-2-amine, 5-(tert-butyl)-2-(1H -imidazol-2-yl)-N-isopropylaniline, 4-(1H-imidazol-2-yl)-N,2',6'-trimethyl-[1,1'-biphenyl]-3-amine, 8-(1H-benzo[d]imidazol-2-yl)-9-H-carbazole-2-carboxynitrile, 10-(1H-benzo[d]imidazol-2-yl)-11H-benzofuran[3,2-b]carbazole and 11-(1H- [Benzo[d]imidazol-2-yl)-12H-benzofurano[3,2-b]phenoxazine] and aryl-trifluoroborate potassium precursors selected from the following list: [(2,6-dimethylphenyl)trifluoro-14-borane potassium salt, (2,6-diisopropylphenyl)trifluoro-14-borane potassium salt and (3,5-diisopropyl-[1,1'-biphenyl]-4-yl)trifluoro-14-borane potassium salt].

[0809] Table 1. Boron ligands synthesized using representative boron process 1

[0810]

[0811]

[0812]

[0813] Representative boron step 2. Add potassium (2,6-diisopropylphenyl)trifluoro-14-borane (1.073 g, 4.003 mmol) to a 50 mL Schlenk tube, dried in an oven with a stir bar. Add anhydrous THF (10.00 mL) under N2 atmosphere. While stirring at room temperature, add trichlorosilane (437 mg, 0.510 mL, 4.02 mmol) via syringe. Continue stirring at room temperature for 2 hours. Weigh 2-(4-(3-(tert-butyl)-5-(4-phenylpyridin-2-yl)phenyl)-1H-benzo[d]imidazol-2-yl)-3-(methylamino)phenol (1.000 g, 1.906 mmol) into a separate 50 mL Schlenk flask. Add anhydrous THF (10.00 mL) under N2 atmosphere. Cool to -78°C, then add n-butyllithium (2.5 M, in hexane, 2.400 mL, 6.000 mmol) dropwise via syringe. Continue stirring at this temperature for 2 hours. The mixtures are then combined via tubing, the cooling bath removed, and the combined mixture is warmed to room temperature while stirring, then heated to 60°C for 16 hours. The mixture is cooled to room temperature, quenched with a saturated aqueous NH4Cl solution, and further diluted with EtOAc and more water. The two phases are stirred for 15 minutes and then transferred to a separatory funnel. The aqueous and organic layers are separated, and the aqueous layer is then extracted with EtOAc (×2). The combined organic layers were washed with water, then with brine, dried over Na2SO4, filtered, concentrated, and purified by silica gel column chromatography to obtain 11-(3-(tert-butyl)-5-(4-phenylpyridin-2-yl)phenyl)-6-(2,6-diisopropylphenyl)-5-methyl-5,6-dihydrobenzo[e]benzo[4,5]imidazo[1,2-c][1,3,2]diazaboranehexane-1-ol (1.0 g, 76% yield) in the form of a colorless solid.

[0814]

[0815] Using representative boron step 2, 11-(3-(tert-butyl)-5-(4-phenylpyridin-2-yl)phenyl)-1H-benzo[d]imidazol-2-yl)-3-(methylamino)phenol and (3,5-diisopropyl-[1,1'-biphenyl]-4-yl)trifluoro-14-borane potassium salt was prepared to 11-(3-(tert-butyl)-5-(4-phenylpyridin-2-yl)phenyl)-6-(3,5-diisopropyl-[1,1'-biphenyl]-4-yl)-5-methyl-5,6-dihydrobenzo[e]benzo[4,5]imidazo[1,2-c][1,3,2]diazaborone-hexane-1-ol was prepared.

[0816]

[0817] Using representative boron step 2, 11-bromo-6-(2,6-diisopropylphenyl)-5-methyl-5,6-dihydrobenzo[e]benzo[4,5]imidazo[1,2-c][1,3,2]diazaborane-1-ol was prepared from 2-(4-bromo-1H-benzo[d]imidazo-2-yl)-3-(methylamino)phenol and potassium salt of (2,6-diisopropylphenyl)trifluoro-14-borane.

[0818]

[0819] Using representative boron step 2, 11-bromo-5-methyl-6-(3,3′′,5,5′′-tetra-tert-butyl-[1,1′:3′,1′′-tert-phenyl]-2′-yl)-l4-borane potassium salt of 2-(4-bromo-1H-benzo[d]imidazol-2-yl)-3-(methylamino)phenol and trifluoro(3,3′′,5,5′′-tetra-tert-butyl-[1,1′:3′,1′′-tert-phenyl]-2′-yl)-5,6-dihydrobenzo[e]benzo[4,5]imidazol[1,2-c][1,3,2-c]diazaborone-hexane-1-ol was prepared from 2-(4-bromo-1H-benzo[d]imidazol[1,2-c][1,3,2-c]diazaborone-hexane-1-ol.

[0820]

[0821] Add 4-(tert-butyl)-N1-(4-(tert-butyl)phenyl)benzene-1,2-diamine hydrochloride (0.455 g, 1.54 mmol), 11-bromo-6-(2,6-diisopropylphenyl)-5-methyl-5,6-dihydrobenzo[e]benzo[4,5]imidazo[1,2-c][1,3,2]diazaboranehexane-1-ol (0.500 g, 1.02 mmol), and sodium tert-butoxide (0.345 g, 3.58 mmol) to a round-bottom flask equipped with a stir bar. Suspend them in toluene (10.2 mL). Place the mixture under a nitrogen atmosphere, then add BINAP (0.128 g, 0.205 mmol) and Pd2(dba)3 (94 mg, 102 μmol). Heat the mixture in a reflux condenser at 110 °C for 16 hours. The mixture was cooled to room temperature and purified by silica gel column chromatography to obtain 6-(2,6-diisopropylphenyl)-5-methyl-5,6-dihydrobenzo[e]benzo[4,5]imidazo[1,2-c][1,3,2]diazaborone-hexane-1-ol (0.433 g, 60.1% yield) as a colorless solid.

[0822]

[0823] A mixture of 4-(tert-butyl)-N1-(4-(tert-butyl)phenyl)phenyl-1,2-diamine hydrochloride (3.0 g, 9.0 mmol) and 11-bromo-5-methyl-6-(3,3′′,5,5′′-tetratert-butyl-[1,1′:3′,1′′-terphenyl]-2′-yl)-5,6-dihydrobenzo[e]benzo[4,5]imidazo[1,2-c][1,3,2]diazaboranehexane-1-ol (5 g, 6.4 mmol) in anhydrous toluene (54 mL) was placed under a nitrogen atmosphere, and then chloro(tritert-butylphosphine)(2′-amino-1,1′-biphenyl-2-yl)palladium(II) ((PtBu)3Pd G2, 0.33 g, 0.64 mmol) and sodium tert-butoxide (1.8 g, 19 mmol) were added. The mixture was heated to 110°C for 10 hours. The mixture was cooled to room temperature, water (5 mL) was added, and the mixture was filtered through a diatomaceous earth plug and washed with DCM. The filtrate was concentrated and purified by silica gel column chromatography to give 3.0 g (51% yield) of 11-((5-(tert-butyl)-2-((4-(tert-butyl)phenyl)amino)phenyl)amino)-5-methyl-6-(3,3'',5,5''-tetratert-butyl-[1,1':3',1''-terphenyl]-2'-yl)-5,6-dihydrobenzo[e]benzo[4,5]imidazo[1,2-c][1,3,2]diazaborone-hexane-1-ol as a colorless solid.

[0824]

[0825] A mixture of 11-((5-(tert-butyl)-2-((4-(tert-butyl)phenyl)amino)phenyl)amino)-6-(2,6-diisopropylphenyl)-5-methyl-5,6-dihydrobenzo[e]benzo[4,5]imidazo[1,2-c][1,3,2]diazaboranehexane-1-ol (345.3 mg, 490.6 μmol) in triethoxymethane (7.271 g, 8.16 mL, 49.06 mmol) was placed under a nitrogen atmosphere. Concentrated (35%) deuterium chloride (73.52 mg, 163.5 μL, 12,000 mol, 1.963 mmol) was added, and the mixture was heated at 100 °C for 1 hour. The mixture was then cooled to room temperature and purified by silica gel column chromatography to obtain 0.116 g (33% yield) of 11-(6-(tert-butyl)-3-(4-(tert-butyl)phenyl)-1H-3l4-benzo[d]imidazol-1-yl)-6-(2,6-diisopropylphenyl)-5-methyl-5,6-dihydrobenzo[e]benzo[4,5]imidazol[1,2-c][1,3,2]diazaborone-hexane-1-ol as a colorless solid.

[0826]

[0827] Triethyl orthoformate (27.4 mL, 24.4 g, 165 mmol) was added to a vial containing 11-((5-(tert-butyl)-2-((4-(tert-butyl)phenyl)amino)phenyl)amino)-5-methyl-6-(3,3'',5,5''-tetratert-butyl-[1,1':3',1''-terphenyl]-2'-yl)-5,6-dihydrobenzo[e]benzo[4,5]imidazo[1,2-c][1,3,2]diazaboranezahexane-1-ol (3.3 g, 3.3 mmol). The resulting solution was placed under a nitrogen atmosphere, and then concentrated hydrochloric acid (0.82 mL, 9.9 mmol) was added. The reaction mixture was heated to 100 °C for 1 hour. LC / MS indicated that the reaction was complete. The mixture was concentrated under reduced pressure to give 3.4 g (99% yield) of 5-(tert-butyl)-1-(4-(tert-butyl)phenyl)-3-(1-hydroxy-5-methyl-6-(3,3'',5,5''-tetratert-butyl-[1,1':3',1''-terphenyl]-2'-yl)-5,6-dihydrobenzo[e]benzo[4,5]imidazo[1,2-c][1,3,2]diazaborone-hexane-11-yl)-1H-benzo[d]imidazo-3-onium chloride.

[0828]

[0829] Representative Ir process 1. The compound was synthesized according to the process reported by Mator et al. in US20200354390, by combining 0.220 g (0.416 mmol) of 9-(3,5-diisopropyl-[1,1′-biphenyl]-4-yl)-9H-benzo[4′,5′]imidazo[1′,2′:3,4][1,3,2]diazaboronehexanocyclo[5,6,1-jk]carbazole with Ir precursor 1 in refluxed 1,2-dichlorobenzene. The crude reaction mixture was purified by silica gel column chromatography to give 0.122 g (56%) of compound 1 of the present invention as a yellow solid.

[0830] The compounds of the present invention listed in Table 2 were synthesized using a representative Ir process 1, with their corresponding ligands selected from the following list: 9-(3,5-diisopropyl-[1,1'-biphenyl]-4-yl)-9H-benzo[4',5']imidazo[1',2':3,4] [1,3,2]diazaboronehexanecyclo[5,6,1-jk]carbazole-6-carboxynitrile, 8-(3,5-diisopropyl-[1,1'-biphenyl]-4-yl)-8H-pyrido[3',2':3,4] [1,2]azaborazhexane[5,6,1-jk]carbazole, 5-(2,6-diisopropylphenyl)-8-(2,6-dimethylphenyl)-6-methyl-5,6-dihydrobenzi[e]imidazo[1,2-c][1,3,2]diazaborazhexane, 5,8-bis(2,6-diisopropylphenyl)-6-methyl-5,6-dihydrobenzi[e]imidazo[1,2-c] [1,3,2]diazaborazhexane, 8-(9H-carbazol-9-yl)-5-(2,6-diisopropylphenyl)-6-methyl-5,6-dihydrobenzi[e]imidazo[1,2-c] [1,3,2]diazaborazhexane, 7-(9H-carbazol-9-yl)-5-(2,6-diisopropylphenyl)-6-methyl-5,6-dihydrobenzi[e]imidazo[1,2-c] [1,3,2]diazaborazhexane, 5-(2,6-diisopropylphenyl)-6-methyl-7-phenyl-5,6-dihydrobenzi[e]imidazo[1,2-c] [1,3,2]diazaborazhexane, 5-(2,6-diisopropylphenyl)-6,7-diphenyl-5,6-dihydrobenzi[e]imidazo[1,2-c] [1,3,2]diazaborone hexane and 8-(tert-butyl)-5-(2,6-diisopropylphenyl)-6-isopropyl-5,6-dihydrobenzo[e]imidazo[1,2-c][1,3,2]diazaborone hexane.

[0831] Table 2. Compounds of the present invention synthesized using representative Ir process 1.

[0832]

[0833]

[0834]

[0835] Representative Ir step 2. Bis(2-(4-(tert-butyl)pyridin-2-yl)phenyl)iridium(III)trifluoromethanesulfonic acid di(methanol) adduct (0.425 g, 0.515 mmol) was combined with 9-(3,5-diisopropyl-[1,1'-biphenyl]-4-yl)-9H-benzo[4',5']imidazo[1',2':3,4][1,3,2]diazaboronehexanocyclo[5,6,1-jk]carbazole (0.300 g, 0.567 mmol) in 1,2-dichlorobenzene (4.0 mL), and the combined reaction mixture was refluxed for 24 hours. The mixture was cooled to room temperature and purified by silica gel column chromatography to obtain 0.013 g (2.1% yield) of the compound 11 of the present invention as a yellow solid.

[0836] The compounds of the present invention listed in Table 3 were synthesized using a representative Ir step 2, with their corresponding ligands selected from the following list: 10-(3,5-diisopropyl-[1,1'-biphenyl]-4-yl)-10H-benzo[4',5']imidazo[1',2':3,4][1,3,2]diazaboronehexano[5,6,1-jk]benzofurano[3,2-b]carbazole, 18-(3,5-diisopropyl-[1,1'-biphenyl]-4-yl)-18H-benzo[4',5']imidazo[1',2':3,4] [1,3,2]diazaboroxacyclohexano[5,6,1-kl]benzofurano[3,2-b]phenoxazine, 8-(3,5-diisopropyl-[1,1'-biphenyl]-4-yl)-8H-pyrido[3',2':3,4] [1,2]diaboroxacyclohexano[5,6,1-jk]carbazole, 8H-[1,6]naphtho[8,7,6-jk]carbazole-8-one, 8,8-diphenyl-8H-pyrido[3',2':3,4][1,2]diasilioxacyclohexano[5,6,1-jk]carbazole, and 8,8-diphenyl-8H-pyrido[3',2':3,4] [1,2]azagermanium cyclohexano[5,6,1-jk]carbazole, and iridium complex precursors selected from the following list: bis(2-(4-(tert-butyl)pyridin-2-yl)phenyl)iridium(III)trifluoromethanesulfonic acid di(methanol) adduct, bis((2-(4-(tert-butyl)pyridin-2-yl)-5-fluorophenyl)iridium(III)bis(methanol) adduct, and bis(2-(5-(tert-butyl)pyridin-2-yl)phenyl)iridium(III)trifluoromethanesulfonic acid di(methanol) adduct.

[0837] Table 3. Compounds of the present invention synthesized using representative Ir process 2.

[0838]

[0839]

[0840] Representative Ir process 3. These compounds were synthesized according to the process reported by Mator et al. in US20200354390, by combining 0.038 g (0.084 mmol) of 5-(2,6-diisopropylphenyl)-8-(2,6-dimethylphenyl)-6-methyl-5,6-dihydrobenzo[e]imidazo[1,2-c][1,3,2]diazaboronexane and 0.027 g (0.084 mmol) of 3,3,4,4-tetramethyl-7-(methyl-d3)-3,4-dihydrodibenzo[b,ij]imidazo[2,1,5-de]quinazine with 0.028 g (0.048 mmol) of Ir precursor 1 in refluxed 1,2-dichlorobenzene. The crude reaction mixture was purified by silica gel column chromatography to obtain 0.005 g (8.2%) of compound 19 of the present invention as a yellow solid and 0.012 g (18%) of compound 20 of the present invention as a yellow solid.

[0841] The compounds of the present invention listed in Table 4 were synthesized using a representative Ir process 3, and their corresponding ligands were selected from the following list: 5,8-bis(2,6-dimethylphenyl)-6-methyl-5,6-dihydrobenzo[e]imidazo[1,2-c][1,3,2]diazaboronexane, 5-(2,6-diisopropylphenyl)-8-(2,6-dimethylphenyl)-6-methyl-5,6-dihydrobenzo[e]imidazo[1,2-c][1,3,2]diazaboronexane, 8-(2,6-diisopropylphenyl) 8-(9H-carbazol-9-yl)-5-(2,6-diisopropylphenyl)-6-methyl-5,6-dihydrobenzo[e]imidazo[1,2-c][1,3,2]diazaborazhexane, 7-(9H-carbazol-9-yl)-5-(2,6-diisopropylphenyl)-6-methyl-5,6-dihydrobenzo[e]imidazo[1,2-c][1,3,2]diazaborazhexane, 7-(9H-carbazol-9-yl)-5-(2,6-diisopropylphenyl)-6-methyl-5,6-dihydrobenzo[e]imidazo[1,2-] c][1,3,2]diazaborone hexane and 8-(tert-butyl)-5-(2,6-diisopropylphenyl)-6-isopropyl-5,6-dihydrobenzo[e]imidazo[1,2-c][1,3,2]diazaborone hexane, and their corresponding auxiliary ligands are selected from the following list: 3,6-ditert-butyl-9-(4-methylpyridin-2-yl)-9H-carbazole, 9-(4,5-dimethylpyridin-2-yl)-9H-carbazole, 9-(4,5-bis(methyl-d3)pyridin-2-yl)-9H- Carbazole, 2-(2,6-diisopropylphenyl)-1,3-diphenyl-2,3-dihydro-1H-[1,3,2]diazabora-pentacyclo[4,5-b]pyridine, 2-(2,6-dimethylphenyl)-7-methyl-1,3-diphenyl-2,3-dihydro-1H-[1,3,2]diazabora-pentacyclo[4,5-b]pyridine, 3,6-di-tert-butyl-9-(4-methylpyridin-2-yl)-9H-carbazole, and 3,6-diethyl-9-(4-methylpyridin-2-yl)-9H-carbazole.

[0842] Table 4. Compounds of the present invention synthesized using representative Ir process 3.

[0843]

[0844]

[0845]

[0846] Representative Pt process 1. 11-(3-(tert-butyl)-5-(4-phenylpyridin-2-yl)phenyl)-6-(3,5-diisopropyl-[1,1'-biphenyl]-4-yl)-5-methyl-5,6-dihydrobenzo[e]benzo[4,5]imidazo[1,2-c][1,3,2]diazaboranehexane-1-ol (0.509 g, 660 μmol), Pt(acac)2 (260 mg, 660 μmol), and acetic acid (6.000 mL) were added to a 50 mL Schlenk tube equipped with a stir bar. The mixture was placed under a N2 atmosphere and then heated under reflux for 16 hours. The mixture was cooled to room temperature and then diluted with MeOH. The resulting precipitate was collected onto a diatomaceous earth bed by vacuum filtration and then dissolved and washed using DCM. The filtrate was then transferred to a separatory funnel, washed with saturated NaHCO3 aqueous solution and brine, dried with Na2SO4, filtered, concentrated, and purified by silica gel column chromatography to obtain 366 mg (56%) of the compound 32 of the present invention as a yellow solid.

[0847] The compounds of the present invention listed in Table 4 were synthesized using a representative Pt step 1, with their corresponding ligands selected from the following list: 11-(3-(tert-butyl)-5-(4-phenylpyridin-2-yl)phenyl)-6-(2,6-diisopropylphenyl)-5-methyl-5,6-dihydrobenzo[e]benzo[4,5]imidazo[1,2-c][1,3,2]diazaborone-hexane-1-ol, 5-(tert-butyl)-1-(4-(tert-butyl)phenyl)-3-(6-(2,6-diisopropylphenyl)-1-hydroxy-5-methyl-5,6-dihydrobenzo[e]benzo[ [4,5]imidazo[1,2-c][1,3,2]diazaborone-hexane-11-yl)-1H-benzo[d]imidazo-3-onium chloride and 5-(tert-butyl)-1-(4-(tert-butyl)phenyl)-3-(1-hydroxy-5-methyl-6-(3,3'',5,5''-tetratert-butyl-[1,1':3',1''--terphenyl]-2'-yl)-5,6-dihydrobenzo[e]benzo[4,5]imidazo[1,2-c][1,3,2]diazaborone-hexane-11-yl)-1H-benzo[d]imidazo-3-onium chloride.

[0848] Table 5. Compounds of the present invention synthesized using representative Pt process 1

[0849]

[0850] Table 6. Photophysical properties of blue light-emitting Ir compounds

[0851]

[0852]

[0853]

[0854]

[0855]

[0856] Table 6 shows the PL λ of the emission spectra in PMMA of compounds 1-3 and compounds 4-10, 19-25 and 27-31 of the present invention. max Photoluminescence quantum yield (PLQY). An overall trend of increasing PLQY can be observed between the comparative compounds and the compounds of the present invention, while maintaining the blue light emission color, through the aryl or heteroaryl substitution on ring B of Formula I. This is evident when comparing the homogeneous comparative compounds 1 (454 nm, 36% PLQY) and 2 (454 nm, 32% PLQY) with the homogeneous compounds of the present invention 4-9 (all ≤472 nm, all ≥59% PLQY). Furthermore, a similar trend can be observed in the heterogeneous comparative compound 3 (484 nm, 51% PLQY) and compounds of the present invention 24 (469 nm, 69% PLQY) and 28 (472 nm, 74% PLQY), where the heteroaryl substitution on ring B of Formula I not only increases PLQY but also achieves a blue shift in λ. max The improvements in these values ​​are greater than those attributable to experimental error, and the observed improvements are significant. These data confirm the unexpected benefits in efficiency and color resulting from aryl or heteroaryl substitution, making the present invention suitable for saturated blue PhOLED applications.

[0857] Table 7. Photophysical properties of green-emitting Ir compounds

[0858]

[0859]

[0860]

[0861] Table 7 shows the PL λ of the emission measured at 77 K in 2-methyltetrahydrofuran solutions of compounds 1-3 and 11-18 of the present invention. max and full width at half maximum (FWHM). Compound 1 of the present invention, with a benzimidazole-linked homogeneous structure (510 nmλ). maxCompounds 11 (511 nm, 15 nm) and 12 (525 nm, 13 nm) of the present invention demonstrate narrow line-shapes in saturated and tunable green light achieved through the boron-linked structures of the present invention. Compounds 14 (520 nm, 22 nm), 17 (525 nm, 17 nm), and 18 (531 nm, 18 nm) of the present invention, in both homogeneous and heterogeneous structures, further demonstrate that the benefits of the features of the present invention extend to achieving tunable and narrow green emission using pyridine A rings and SiR2 or GeR2 linkers. In summary, the data in Table 7 provide a variety of strategies for modifying PhOLED materials by line-shape or color tuning, making the present invention suitable for green PhOLED applications.

[0862] Table 8. Photophysical properties of green-emitting Pt compounds

[0863]

[0864] Table 8 shows the comparison results for compound 8 (503 nm λ). max The emission peaks (PL λ) of compounds 32-33 of the present invention in 2-methyltetrahydrofuran solution measured at 77 K at 24 nm FWHM were compared with those of the present invention. max The full width at half maximum (FWHM) values ​​were 504 nm and 22 nm, respectively; and 503 nm and 22 nm, respectively. These data confirm that the BN-connected structure of the present invention can achieve comparable T1 emission colors (saturated green), but with the added benefit of a narrower lineshape (2 nm), thus providing improved color purity. These improvements are greater than those attributable to experimental error, and the observed improvements are significant. This benefit makes the present invention suitable for saturated green PhOLED applications.

[0865] Emission spectra were collected on a Horiba Fluorolog-3 spectrophotometer equipped with a Synapse Plus CCD detector. All samples were excited at 340 nm. A solution of 1% emitter with PMMA in toluene was prepared, filtered, and drop-coated onto a quartz substrate.

[0866] OLED devices are manufactured using the following material group.

[0867]

[0868]

[0869]

[0870] OLEDs were grown on a glass substrate pre-coated with an indium tin oxide (ITO) layer having a sheet resistance of 15 Ω / sq. Before any organic layer deposition or coating, the substrate was degreased with a solvent, then treated with oxygen plasma at 50 W for 1.5 minutes at 100 mTorr, followed by UV ozone treatment for 5 minutes. The OLEDs were then grown by thermal evaporation in a high vacuum (<10) environment. -6 The device was fabricated in a Torr atmosphere. The anode electrode was 750 Å indium tin oxide (ITO). Immediately after fabrication, all devices were encapsulated with glass lids and sealed with epoxy resin in a nitrogen glove box (<1 ppm H2O and O2), with a desiccant incorporated inside the encapsulation. Doping percentages are expressed as volume percentages.

[0871] Two devices were used to grow organic layers, which, starting from the ITO surface, sequentially comprised: 100 Å of compound 1 (HIL), 250 Å of compound 2 (HTL), 50 Å of HHost (EBL), EML, 50 Å of EHost (BL), 300 Å of compound 5 doped with 35% compound 6 (ETL), 10 Å of compound 5 (EIL), followed by 1000 Å of Al (cathode). The composition of the EML is shown in Table 1.

[0872] Table 1: EML composition and electroluminescence wavelength at maximum intensity (λ) max )

[0873]

[0874] Compounds 34 and 35 of this invention both exhibit deep blue emission in OLED devices, wherein λ max The wavelengths (nm) are 455nm and 452.5nm, respectively. This color point in a blue OLED is essential for meeting the specifications required for high color purity display applications. Compound 35 of this invention, with its larger substituents attached to boron atoms, exhibits a higher energy λ. max This illustrates the importance of spatial steric hindrance in achieving the deep blue dot.

Claims

1. A compound having a first ligand L comprising the structure of formula I. A : Equation I; Structural parts A and B are each independently a single-ring or multi-ring fused ring system, wherein each ring in the single-ring or multi-ring fused ring system is independently a 5- to 10-membered carbon ring or heterocyclic ring. Where K 1 and K 2 Each is independently selected from direct bonds, O, S, N(R) α ), P(R α ), B(R) α ), C(R α (R) β ) and Si(R α (R) β ); Z 1 Selected from BR C C=O, C=S, C=Se, GaR C SiR C R C′ and GeR C R C′ ; Z 2 Selected from NR D O and S; Where X 1 To X 5 Each can be independently represented as C or N; Where R A and R B Each can be independently represented from single substitution to the maximum permissible substitution or no substitution; Where R α R β R A R B R C and R D Independently hydrogen or a substituent selected from the following: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silalkyl, germanalkyl, boronalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphinyl, boronyl, selenyl, and combinations thereof; Where R α R β R A R B R C and R D Any two of them can join or fuse to form a ring; in Is it a single bond or a double bond? Where L A Fit to metal M; Metal M can coordinate with other ligands; Where L A It can bind to other ligands to include tridentate, tetradentate, pentadentate or hexadentate ligands; The condition is that when M is Ir, Z 1 It is BR C And Z 2 It is NR D When, then R A and from Z 1 R C They do not join together to form 5- or 6-membered rings, and originate from Z. 1 R C and from Z 2 R D They do not combine to form 5- or 6-membered rings; and At least one of the following eleven conditions is true: 1) Structural part A is a 6- to 10-member ring, and X 5 R on B and from Z 2 R D Joining to form a multi-ring fused ring system, and X 4 Not N; 2) Structural part A is a 5-membered ring, Z 2 It is NR D X 5 R on B and from Z 2 R D Joining to form a multi-ring fused ring system, and X 4 It's not N, the condition is if Z 1 It is BR C Structural part A is imidazole, and X 1 and X 3 If it is N, then by R B and from Z 2 R D The resulting polycyclic fused ring system is neither tetrahydroquinoline nor unsubstituted carbazole; 3) M is Pt or Pd, and the structural part A is a 6-membered ring; 4) Structural part A is a 6-membered ring, X 3 It is N, and Z 1 Selected from BR C GaR C SiR C R C’ and GeR C R C’ ; 5) Structural part B is a 6-membered ring, X 4 It is N, and Z 1 Selected from BR C GaR C SiR C R C’ and GeR C R C’ The condition is that if Z 2 It is NR D Then R D and from X 5 R B Non-jointing forms a ring; 6) Both structural part A and structural part B are 6-membered rings, Z 1 Selected from C=O, C=S, and C=Se, and Z 2 It is NR D The condition is that if M is Ir, then R D It is a cyclic group; 7) R A R B R C (If it exists) and R D At least one of them (if present) includes a group selected from germanyl, boranyl and partially or fully deuterated silyl groups; 8) R A R B R C (If it exists) and R D At least one of them (if it exists) includes three 6-membered aromatic rings that are not fused together with each other, or an aromatic ring fused with a non-aromatic ring. 9) Structural part A is a 5-membered ring and Z 1 Selected from C=O, C=S, and C=Se; 10) M is Pt or Pd, X 1 and X 3 Both are N, X 2 It is C, structural part A is an imidazole ring, and the two Rs A Joining to form a further substituted benzene ring; and 11) The compound contains The structure and at least one of the following three conditions is true: (i) at least one R B It is neither hydrogen nor CH3, (ii)X 5 To X 9 At least one of them is N, and (iii)R D It exists and is a heteroaryl group or contains at least one electron-withdrawing group, provided that X 5 To X 9 If both are C, then R C and R D Non-joint formation of a 6-membered ring and R D no or ; And the compound described is not one of the following compounds: , , , , , , , , , , , and .

2. The compound according to claim 1, when M is Ir, Z 1 It is BR C And Z 2 It is NR D When, then R A and from Z 1 R C They do not join together to form 5- or 6-membered rings, and originate from Z. 1 R C and from Z 2 R D They do not join together to form a 5- or 6-membered ring; and / or where Z 2 It is NR D R D It includes a multi-ring fused ring system, and R D and X 5 R on B Joined together to form a 5 to 10-membered ring; and / or where R D Selected from naphthalene, quinoline, isoquinoline, quinazoline, quinoxaline, benzofuran, aza-benzofuran, benzoxazole, aza-benzoxazole, benzothiophene, aza-benzothiophene, benzothiazole, aza-benzothiazole, benzoselenophenol, aza-benzoselenophene, indene, aza-indene, indole, aza-indole, benzimidazole, aza-benzimidazole, carbazole, aza-carbazole, naphthemidazole (benzobenzimidazole), dibenzofuran, aza-dibenzofuran, dibenzothiphene, aza-dibenzothiphene, phthalazine, phenanthrene, aza-phenanthrene, anthracene, aza-anthracene, phenanthridine, fluorene, and aza-fluorene; and / or R D and X 5 R on B Joined together to form a 5-membered ring; and / or where R D and X 5 R on B They are joined together to form a 6-membered ring.

3. The compound according to claim 1, wherein structural moiety A is a 6- to 10-membered ring, and X 5 R on B and Z 2 R on D Joining to form a multi-ring fused ring system, and X 4 Not N; or The structural part A is a 5-membered ring, Z 2 It is NR D X 5 R on B and from Z 2 R D Joining to form a multi-ring fused ring system, and X 4 It's not N, the condition is if Z 1 It is BR C Then structural part A is imidazole, and X 1 and X 3 If it is N, then by R B and from Z 2 R D The resulting polycyclic fused ring system is not tetrahydroquinoline or unsubstituted carbazole; and / or Where R A R B R C (If it exists) and R D At least one of them (if present) includes a group selected from germanyl, boronyl, and partially or fully deuterated silyl groups; and / or wherein R A R B R C (If it exists) and R D At least one of them (if present) includes three 6-membered aromatic rings that are not fused together with each other, or an aromatic ring fused with a non-aromatic ring.

4. The compound according to claim 1, wherein one of conditions 10) and 11) is true: 10) M is Pt or Pd, X 1 and X 3 Both are N, X 2 It is C, structural part A is an imidazole ring, and the two Rs A To combine to form a further substituted benzene ring; or 11) The compound contains The structure and at least one of the following three conditions is true: (i) at least one R B It is neither hydrogen nor CH3, (ii)X 5 To X 9 At least one of them is N, and (iii)R D It exists and is a heteroaryl group or contains at least one electron-withdrawing group, provided that X 5 To X 9 If both are C, then R C and R D Non-joint formation of a 6-membered ring and R D no or .

5. The compound according to claim 1, wherein the ligand L A Selected from the structure of LIST 1 as defined in this paper; Where X 6 To X 19 Each can be independently represented as C or N; Z 3 and Z 4 Each is independently selected from O, S, and NR. a C(R) a (R) b ) and Si(R a (R) b );and Each R', R a R b R AA R BB R CC and R DD Independently hydrogen or a substituent selected from the following: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silalkyl, germanalkyl, boronalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphinyl, boronyl, selenyl, and combinations thereof.

6. The compound according to claim 1, wherein the ligand L A The structure is selected from LIST 2 as defined in this paper.

7. The compound according to claim 1, wherein the ligand L A Selected from L A W1-(R i (R) j (R) k (R) l ) and L A W2-(R j (R) k (R) l ), where W1 is an integer from 1 to 263, 265, 267 to 280, 282, 284 to 489, W2 is 264, 266, 281, and 283, and each i, j, k, and l is an integer from 1 to 263, R i R j R k and R l Each is independently selected from V1 to V263, and L A W1-(R i (R) j (R) k (R) l ) and L A W2-(R j (R) k (R) l Each is as defined in the table of LIST 3 as defined in this article; V1 to V263 have the structure of LIST A as defined in this paper.

8. The compound of claim 1, wherein the compound is selected from the structures in LIST 9 as defined herein; and / or wherein the compound is selected from the structures in LIST 16 as defined herein.

9. The compound according to claim 1, wherein the compound comprises the structure of formula II: Formula II, in: M 1 It is either Pd or Pt; X 20 Z 5 and X 21 Optionally joined or fused into structural part E; X 22 Z 6 and X 23 Optionally joined or fused into structural part F; Structural part E (if it exists) is optionally controlled by R E Substitution, which refers to single substitution to the maximum permissible substitution; The structural part F (if it exists) is optionally controlled by R. F Substitution, which refers to single substitution to the maximum permissible substitution; Structural parts E (if present) and F (if present) are each independently a monocyclic ring or a polycyclic fused ring system, wherein each ring of the monocyclic ring or the polycyclic fused ring system is independently a 5- to 10-membered carbon ring or a heterocyclic ring. X 20 To X 23 Each can be independently represented as C or N; Z 5 and Z 6 Each can be independently represented as C or N; K 1 K 2 K 3 and K 4 Each is independently selected from direct bonds, O, S, N(R) α ), P(R α ), B(R) α ), C(R α (R) β ) and Si(R α (R) β ), where at least two of them are direct bonds; Two adjacent R A R B R E and R F They can be joined or fused together, where chemically feasible, to form a ring; and Z 1 Z 2 Structural part A, Structural part B, R A R B R C and R D The definitions are all the same as those above; among which Indicates a single or double bond; where X 20 L 1 and X 7 Between Indicates a direct key or no key; where X 23 L 3 and X 10 Between Indicates a direct key or no key; L 1 L 2 and L 3 Each is independently selected from single bond, non-existent bond, BR, BRR', NR, PR, P(O)R, O, S, Se, C=O, C=S, C=Se, C=NR, C=CRR', S=O, SO2, CR, CRR', SiRR', and GeRR', among which L exists. 1 and L 3 At least one of them; Where L 1 When it exists, L 1 Selected from direct bonds, BR, BRR′, NR, PR, P(O)R, O, S, Se, C=O, C=S, C=Se, C=NR, C=CRR', S=O, SO2, CR, CRR′, SiRR′, and GeRR′, where L 3 When it exists, L 3 Selected from direct bonds, BR, BRR′, NR, PR, P(O)R, O, S, Se, C=O, C=S, C=Se, C=NR, C=CRR', S=O, SO2, CR, CRR′, SiRR′, and GeRR′. R, R′, R E (If it exists) and R F Each of (if present) is independently hydrogen or a substituent selected from the following: deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silalkyl, germanalkyl, boroalkyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thioyl, and combinations thereof. And at least one of the following eleven conditions is true: 1) Structural part A is a 6- to 10-member ring, and X 5 R on B and from Z 2 R D Joining to form a multi-ring fused ring system, and X 4 Not N; 2) Structural part A is a 5-membered ring, Z 2 It is NR D X 5 R on B and from Z 2 R D Joining to form a multi-ring fused ring system, and X 4 It's not N, the condition is if Z 1 It is BR C Structural part A is imidazole, and X 1 and X 3 If it is N, then by R B and from Z 2 R D The resulting polycyclic fused ring system is neither tetrahydroquinoline nor unsubstituted carbazole; 3) Structural part A is a 6-membered ring; 4) Structural part A is a 6-membered ring, X 3 It is N, and Z 1 Selected from BR C GaR C SiR C R C’ and GeR C R C’ ; 5) Structural part B is a 6-membered ring, X 4 It is N, and Z 1 Selected from BR C GaR C SiR C R C’ and GeR C R C’ The condition is that if Z 2 It is NR D Then R D and from X 5 R B Non-jointing forms a ring; 6) Both structural part A and structural part B are 6-membered rings, Z 1 Selected from C=O, C=S, and C=Se, and Z 2 It is NR D The condition is that if M is Ir, then R D It is a cyclic group; 7) R A R B R C (If it exists) and R D At least one of them (if present) includes a group selected from germanyl, boranyl and partially or fully deuterated silyl groups; 8) R A R B R C (If it exists) and R D At least one of them (if it exists) includes three 6-membered aromatic rings that are not fused together with each other, or an aromatic ring fused with a non-aromatic ring. 9) Structural part A is a 5-membered ring and Z 1 Selected from C=O, C=S, and C=Se; 10) X 1 and X 3 Both are N, X 2 It is C, structural part A is an imidazole ring, and the two Rs A They combine to form a benzene ring that is further substituted; as well as 11) The compound contains The structure and at least one of the following three conditions is true: (i) at least one R B It is neither hydrogen nor CH3, (ii)X 5 To X 9 At least one of them is N, and (iii)R D It exists and is a heteroaryl group or contains at least one electron-withdrawing group, provided that X 5 To X 9 If both are C, then R C and R D Non-joint formation of a 6-membered ring and R D no or ; And the compound described is not one of the following compounds: , , , , , , , , and .

10. The compound according to claim 9, wherein the compound is selected from the group having the formula Pt(L A’ (L) y Compounds of: Where L A’ Selected from the structure shown in LIST 10 as defined in this document; Where L y Selected from the structure shown in LIST 13 as defined in this document; Each R X and R Y Independently hydrogen or a substituent selected from the following: deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silalkyl, germanalkyl, boroalkyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thioyl, and combinations thereof.

11. The compound according to claim 1, wherein the compound is selected from the group having the formula Pt(L A’ (L) y Compounds of: Where L A’ Selected from L A’ Q1-(R i (R) j (R) k (R) l ), L A’ Q2-(R j (R) k (R) l) , L A’ Q3-(R j (R) k (R) l (R) m ), L A’ Q4-(R i (R) j (R) k (R) n ), L A’ Q5-(R i (R) k (R) l (R) m ), L A’ Q6-(R k (R) l (R) m (R) o ),L A’ Q7-(R j (R) k (R) n ), L A’ Q8-(R i (R) k) (R l (R) o ), L A’ Q9-(R j (R) l (R) m (R) n Q1 is an integer from 1 to 15, 17 to 19, 21 to 27, 29 to 259, 261, 263 to 276, 278, 280 to 366, 367 to 372, 376, and 396 to 400; Q2 is an integer from 16, 20, 28, 260, 262, 277, 279, 391, and 393; Q3 is an integer from 373 to 375, 378 to 382, ​​384, 385, and 401 to 406; Q4 is 377; Q5 is 383 and 386; Q6 is 387 to 390 and 394; Q7 is 392; Q8 is 395; Q9 is 407; each i , j , k , m , n , o ,and l Independently, R represents integers from 1 to 468; i R j R k R l R m R n and R o Each of the L1 to R468 is independently selected from R1 to R468, where R1 to R468 are as defined in LIST 12, and each L A’ The structure is as defined in the LIST 14 table as defined in this article; Where L y Selected from L y Z1-(R s (R) t (R) u ), L y Z2-(R p (R) q (R) r (R) s ), L y Z3-(R q (R) r (R) s ),L y Z4-(R p (R) q (R) r (R) t ), L y Z5-(R p (R) q (R) r (R) u ), L y Z6-(R q (R) r (R) u ), L y Z7-(R p (R) q (R) s (R) v ), L y Z8-(R q (R) s (R) v ), L y Z9-(R s (R) v (R) t ), L y Z10-(R p (R) q (R) s (R) v (R) t ),L y Z11-(R p (R) s (R) v ), L y Z12-(R p (R) s (R) v (R) t Z1 is an integer from 1 to 95; Z2 is an integer from 96 to 98, 102 to 111, 116, 120, and 121; Z3 is an integer from 99, 113, 117 to 119, and 122; Z4 is 100, 101, and 115; Z5 is 112; Z6 is 114; Z7 is 123 and 124; Z8 is 125; Z9 is 126; Z10 is 127; Z11 is 128 and 129; Z12 is 130; each p, q, r, s, t, u, and v is independently an integer from 1 to 468, R p R q R r R s R t R u and R v Each of them is independently selected from R1 to R468, and each L y The structure is as defined in the LIST 15 table as described in this article; R1 to R468 have the structure defined in LIST 12 as defined in this paper.

12. An organic light-emitting device (OLED), comprising: anode; cathode; as well as An organic layer disposed between the anode and the cathode The organic layer comprises having a first ligand L A The compound, the first ligand L A Structure of Formula I: Equation I; Structural parts A and B are each independently a single-ring or multi-ring fused ring system, wherein each ring in the single-ring or multi-ring fused ring system is independently a 5- to 10-membered carbon ring or heterocyclic ring. Where K 1 and K 2 Each is independently selected from direct bonds, O, S, N(R) α ), P(R α ), B(R) α ), C(R α (R) β ) and Si(R α (R) β ); Z 1 Selected from BR C C=O, C=S, C=Se, GaR C SiR C R C′ and GeR C R C′ ; Z 2 Selected from NR D O and S; Where X 1 To X 5 Each can be independently represented as C or N; Where R A and R B Each can be independently represented from single substitution to the maximum permissible substitution or no substitution; Where R α R β R A R B R C and R D Independently hydrogen or a substituent selected from the following: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silalkyl, germanalkyl, boronalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphinyl, boronyl, selenyl, and combinations thereof; Where R α R β R A R B R C and R D Any two of them can join or fuse to form a ring; in Is it a single bond or a double bond? Where L A Fit to metal M; Metal M can coordinate with other ligands; Where L A It can bind to other ligands to include tridentate, tetradentate, pentadentate or hexadentate ligands; The condition is that when M is Ir, Z 1 It is BR C And Z 2 It is NR D When, then R A and from Z 1 R C They do not join together to form 5- or 6-membered rings, and originate from Z. 1 R C and from Z 2 R D They do not combine to form 5- or 6-membered rings; and At least one of the following eleven conditions is true: 1) Structural part A is a 6- to 10-member ring, and X 5 R on B and from Z 2 R D Joining to form a multi-ring fused ring system, and X 4 Not N; 2) Structural part A is a 5-membered ring, Z 2 It is NR D X 5 R on B and from Z 2 R D Joining to form a multi-ring fused ring system, and X 4 It's not N, the condition is if Z 1 It is BR C Structural part A is imidazole, and X 1 and X 3 If it is N, then by R B and from Z 2 R D The resulting polycyclic fused ring system is neither tetrahydroquinoline nor unsubstituted carbazole; 3) M is Pt or Pd, and the structural part A is a 6-membered ring; 4) Structural part A is a 6-membered ring, X 3 It is N, and Z 1 Selected from BR C GaR C SiR C R C’ and GeR C R C’ ; 5) Structural part B is a 6-membered ring, X 4 It is N, and Z 1 Selected from BR C GaR C SiR C R C’ and GeR C R C’ The condition is that if Z 2 It is NR D Then R D and from X 5 R B Non-jointing forms a ring; 6) Both structural part A and structural part B are 6-membered rings, Z 1 Selected from C=O, C=S, and C=Se, and Z 2 It is NR D The condition is that if M is Ir, then R D It is a cyclic group; 7) R A R B R C (If it exists) and R D At least one of them (if present) includes a group selected from germanyl, boranyl and partially or fully deuterated silyl groups; 8) R A R B R C (If it exists) and R D At least one of them (if it exists) includes three 6-membered aromatic rings that are not fused together with each other, or an aromatic ring fused with a non-aromatic ring. 9) Structural part A is a 5-membered ring and Z 1 Selected from C=O, C=S, and C=Se; 10) M is Pt or Pd, X 1 and X 3 Both are N, X 2 It is C, structural part A is an imidazole ring, and the two Rs A They combine to form a benzene ring that is further substituted; and 11) The compound contains The structure and at least one of the following three conditions is true: (i) at least one R B It is neither hydrogen nor CH3, (ii)X 5 To X 9 At least one of them is N, and (iii)R D It exists and is a heteroaryl group or contains at least one electron-withdrawing group, provided that X 5 To X 9 If both are C, then R C and R D Without combining to form a 6-membered ring and R D no or ; And the compound described is not one of the following compounds: , , , , , , , , , , , and .

13. The OLED of claim 12, wherein the organic layer is an emission layer and the compound is an emission dopant or sensitizer, wherein when the compound is a sensitizer, the OLED further comprises a receptor selected from fluorescent emitters, delayed fluorescent emitters, and combinations thereof.

14. A consumer product comprising an organic light-emitting device (OLED), the organic light-emitting device including: anode; cathode; as well as An organic layer disposed between the anode and the cathode The organic layer thereof comprises the compound of claim 1.

15. A compound, or its neutral molecular form, or its monovalent or polyvalent form, or its monomeric or polymeric form, or its macromolecular or supramolecular form; wherein the compound has a first ligand L comprising the structure of formula I. A : Equation I; Structural parts A and B are each independently a single-ring or multi-ring fused ring system, wherein each ring in the single-ring or multi-ring fused ring system is independently a 5- to 10-membered carbon ring or heterocyclic ring. Where K 1 and K 2 Each is independently selected from direct bonds, O, S, N(R) α ), P(R α ), B(R) α ), C(R α (R) β ) and Si(R α (R) β ); Z 1 Selected from BR C C=O, C=S, C=Se, GaR C SiR C R C′ and GeR C R C′ ; Z 2 Selected from NR D O and S; Where X 1 To X 5 Each can be independently represented as C or N; Where R A and R B Each can be independently represented from single substitution to the maximum permissible substitution or no substitution; Where R α R β R A R B R C and R D Independently hydrogen or a substituent selected from the following: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silalkyl, germanalkyl, boronalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphinyl, boronyl, selenyl, and combinations thereof; Where R α R β R A R B R C and R D Any two of them can join or fuse to form a ring; in Is it a single bond or a double bond? Where L A Fit to metal M; Metal M can coordinate with other ligands; Where L A It can bind to other ligands to include tridentate, tetradentate, pentadentate or hexadentate ligands; The condition is that when M is Ir, Z 1 It is BR C And Z 2 It is NR D When, then R A and from Z 1 R C They do not join together to form 5- or 6-membered rings, and originate from Z. 1 R C and from Z 2 R D They do not combine to form 5- or 6-membered rings; and At least one of the following eleven conditions is true: 1) Structural part A is a 6- to 10-member ring, and X 5 R on B and from Z 2 R D Joining to form a multi-ring fused ring system, and X 4 Not N; 2) Structural part A is a 5-membered ring, Z 2 It is NR D X 5 R on B and from Z 2 R D Joining to form a multi-ring fused ring system, and X 4 It's not N, the condition is if Z 1 It is BR C Structural part A is imidazole, and X 1 and X 3 If it is N, then by R B and from Z 2 R D The resulting polycyclic fused ring system is neither tetrahydroquinoline nor unsubstituted carbazole; 3) M is Pt or Pd, and the structural part A is a 6-membered ring; 4) Structural part A is a 6-membered ring, X 3 It is N, and Z 1 Selected from BR C GaR C SiR C R C’ and GeR C R C’ ; 5) Structural part B is a 6-membered ring, X 4 It is N, and Z 1 Selected from BR C GaR C SiR C R C’ and GeR C R C’ The condition is that if Z 2 It is NR D Then R D and from X 5 R B Non-jointing forms a ring; 6) Both structural part A and structural part B are 6-membered rings, Z 1 Selected from C=O, C=S, and C=Se, and Z 2 It is NR D The condition is that if M is Ir, then R D It is a cyclic group; 7) R A R B R C (If it exists) and R D At least one of them (if present) includes a group selected from germanyl, boranyl and partially or fully deuterated silyl groups; 8) R A R B R C (If it exists) and R D At least one of them (if it exists) includes three 6-membered aromatic rings that are not fused together with each other, or an aromatic ring fused with a non-aromatic ring. 9) Structural part A is a 5-membered ring and Z 1 Selected from C=O, C=S, and C=Se; 10) M is Pt or Pd, X 1 and X 3 Both are N, X 2 It is C, structural part A is an imidazole ring, and the two Rs A Joining to form a further substituted benzene ring; and 11) The compound contains The structure and at least one of the following three conditions is true: (i) at least one R B It is neither hydrogen nor CH3, (ii)X 5 To X 9 At least one of them is N, and (iii)R D It exists and is a heteroaryl group or contains at least one electron-withdrawing group, provided that X 5 To X 9 If both are C, then R C and R D Non-joint formation of a 6-membered ring and R D no or ; And the compound described is not one of the following compounds: , , , , , , , , , , , and .

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