Organic electroluminescent materials and devices

Abstract

The invention relates to organic electroluminescent materials and devices. A compound having a first ligand LA comprising a structure of formula I # imgabs0 # wherein at least one of a moiety B or a moiety C has a structure of formula II # imgabs1 # fused thereto. In the compound, each of moieties A and B is a carbocyclic or heterocyclic ring; each of part D, part E and, if present, part C is a monocyclic or polycyclic fused ring system; if part A is a 6-membered ring and part B is a 5-membered ring, part C is present; each of Z1 to Z6 is independently C or N; l1 is a direct bond or a linking group; y is a linking group; each of K1 and K2 is a direct bond or a linking group; each substituent is hydrogen or a universal substituent as defined herein; and LA is coordinated with the metal M. Formulations, OLEDs, and consumer products containing the compounds are also provided.

Description

[0001] Cross - Reference to Related Applications

[0002] This application claims priority to the following U.S. Provisional Applications under 35 U.S.C. § 119(e): Ser. No. 63 / 632,362, filed Apr. 10, 2024; Ser. No. 63 / 619,914, filed Jan. 11, 2024; Ser. No. 63 / 619,527, filed Jan. 10, 2024; Ser. No. 63 / 618,688, filed Jan. 8, 2024; Ser. No. 63 / 614,848, filed Dec. 26, 2023; and Ser. No. 63 / 609,996, filed Dec. 14, 2023, the entire contents of each of which are incorporated herein by reference. TECHNICAL FIELD

[0003] The present disclosure generally relates to organic or metal coordination compounds and formulations 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 OF THE DISCLOSURE

[0004] For various reasons, optoelectronic devices that utilize organic materials have become increasingly popular. Many of the materials used to fabricate such devices are relatively inexpensive, so organic optoelectronic devices have the potential for cost advantages over inorganic devices. Additionally, the inherent properties of organic materials, such as their flexibility, can make them more suitable for certain 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 have performance advantages over conventional materials.

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

[0006] One application of emissive molecules is full-color displays. Industry standards for such displays require pixels that are suitable for emitting specific colors (referred to as “saturated” colors). Specifically, these standards require saturated red, green, and blue pixels. Alternatively, an OLED 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 emissions. The same technique can be used for OLEDs. White OLEDs can be single-emission layer (EML) devices or stacked structures. Color can be measured using CIE coordinates well known in the art. SUMMARY OF THE DISCLOSURE

[0007] In one aspect, the present disclosure provides a compound having a first ligand LA a compound, wherein the first ligand L A comprises the structure of Formula I: wherein at least one of moiety B or moiety C has fused thereto the structure of Formula II In Formula I and Formula II:

[0008] Each of moiety A and moiety B is independently a 5- to 10-membered carbocyclic or heterocyclic ring;

[0009] Each of moiety D, moiety E and (if present) moiety C is independently a monocyclic or polycyclic fused ring system, wherein each ring of the monocyclic or polycyclic fused ring system is independently a 5- to 10-membered carbocyclic or heterocyclic ring;

[0010] If moiety A is a 6-membered ring and moiety B is a 5-membered ring, then moiety C is present;

[0011] Z 1 to Z 6 are each independently C or N;

[0012] L 1 is selected from the group consisting of: a direct 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';

[0013] Y is selected from the group consisting of: 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';

[0014] K 1 and K 2 are each independently selected from the group consisting of: a direct bond, O, S, N(R α ), P(R α ), B(R α ), C(R α )(R β ) and Si(R α )(R β );

[0015] R A 、R B 、R C 、R D and R E each independently represents mono-substitution to the maximum allowable substitution or no substitution;

[0016] R, R', R * 、Rα , R β , R A , R B , R C , R D and R E are each independently hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, seleno, and combinations thereof;

[0017] L A is coordinated with metal M;

[0018] Metal M has an atomic mass of at least 40 and is capable of coordinating with other ligands;

[0019] L A can be joined with other ligands to form a tridentate, tetradentate, pentadentate or hexadentate ligand; and

[0020] any two substituents can be joined or fused to form a ring, provided that the compound is not:

[0021]

[0022] In another aspect, the present disclosure provides a formulation comprising a compound having a first ligand L A wherein the first ligand comprises the structure of Formula I as described herein.

[0023] In another aspect, the present disclosure provides an OLED having an organic layer, the organic layer comprising a compound having a first ligand L A wherein the first ligand comprises the structure of Formula I as described herein.

[0024] In another aspect, the present disclosure provides a consumer product comprising an OLED having an organic layer, the organic layer comprising a compound having a first ligand L A wherein the first ligand comprises the structure of Formula I as described herein. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 Shows an organic light emitting device.

[0026] Figure 2 Shows an inverted organic light emitting device without an independent electron transport layer. DETAILED DESCRIPTION

[0027] A. TERMS

[0028] Unless otherwise specified, the following terms used herein are defined as follows:

[0029] As used herein, "top" means farthest from the substrate, and "bottom" means closest to the substrate. Where a first layer is described as being "disposed over" a second layer, the first layer is disposed farther from the substrate. Unless it is specified that the first layer is "in contact with" the second layer, other layers may be present between the first and second layers. For example, even if various organic layers are present between the cathode and the anode, the cathode can still be described as being "disposed over" the anode.

[0030] As used herein, "solution processable" means capable of being dissolved, dispersed, or transported in a liquid medium in the form of a solution or a suspension and / or deposited from a liquid medium.

[0031] As used herein, and as would be generally understood by one of ordinary skill in the art, if a first energy level is closer to the vacuum level, then the first "highest occupied molecular orbital" (HOMO) or "lowest unoccupied molecular orbital" (LUMO) energy level is "greater than" or "higher than" a second HOMO or LUMO energy level. Since the ionization potential (IP) is measured as a negative energy relative to the vacuum level, a higher HOMO energy level corresponds to an IP with a smaller absolute value (a less negative IP). Similarly, a higher LUMO energy level corresponds to an electron affinity (EA) with a smaller absolute value (a less negative EA). On a conventional energy level diagram where the top is the vacuum level, the LUMO energy level of a material is higher than the HOMO energy level of the same material. A "higher" HOMO or LUMO energy level appears closer to the top of this diagram than a "lower" HOMO or LUMO energy level.

[0032] As used herein, and as would be generally understood by one of ordinary skill in the art, if a first work function has a higher absolute value, then the first work function is "greater than" or "higher than" a second work function. Since the work function is typically measured as a negative number relative to the vacuum level, this means that a "higher" work function is more negative. On a conventional energy level diagram where the top is the vacuum level, a "higher" work function is illustrated as being farther from the vacuum level in the downward direction. Thus, the definitions of HOMO and LUMO energy levels follow a different convention than the work function.

[0033] The present disclosure may describe layers, materials, regions, and devices in terms of the color of the light they emit. Generally, as used herein, an emission region described as producing a particular color of light may include one or more emission layers disposed over one another in a stacked manner.

[0034] As used herein, "NIR", "red", "green", "blue", "yellow" layers, materials, regions or devices refer to layers, materials, regions or devices that emit light within the wavelength ranges of approximately 700 - 1500 nm, 580 - 700 nm, 500 - 600 nm, 400 - 500 nm, 540 - 600 nm, respectively, or layers, materials, regions or devices having the highest emission spectral peak within the corresponding wavelength regions. In some arrangements, separate regions, layers, materials or devices may provide separate "dark blue" and "light blue" emissions. As used herein, a "dark blue" emission component refers to an emission having a peak emission wavelength that is at least about 4 nm less than the peak emission wavelength of a "light blue" emission component. Typically, the peak emission wavelength of the "light blue" emission component is in the range of about 465 - 500 nm, and the peak emission wavelength of the "dark blue" emission component is in the range of about 400 - 470 nm, although these ranges may vary for some configurations.

[0035] In some arrangements, a color-changing layer is provided that converts, modifies or alters the color of light emitted by another layer into an emission having a different wavelength. This color-changing layer can be formulated to shift the wavelength of the light emitted by another layer by a defined amount, as measured 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 photons. For example, a "red" filter may be present to filter the input light to remove light having wavelengths outside the range of about 580 - 700 nm. A "component" of "color" refers to a component that, when activated or used, produces or otherwise emits light having a specific color as previously described. 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 previously described when activated within a device.

[0036] As used herein, emission materials, layers and regions can be distinguished from each other and from other structures based on the light initially produced by the material, layer or region being distinct from the light ultimately emitted by the same or a different structure. Initial light production is typically the result of a change in energy level that leads to photon emission. For example, an organic emission material may initially produce blue light, which can be converted into red or green light by a color filter, quantum dots or other structures, such that the complete emission stack or sub-pixel emits red or green light. In this case, the initial emission material, region or layer can be referred to as the "blue" component, even though the sub-pixel is a "red" or "green" component.

[0037] In some cases, it may be preferable to describe the color of the components, such as the color of the emission region, sub-pixels, color-changing layer, etc., according to the 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. Thus, as used herein, each color term 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 locus between two color points and any other internal points. For example, the internal shape parameters for red, green, blue, and yellow can be defined as follows:

[0038]

[0039] The terms "halo", "halogen", and "halo group" may be used interchangeably and refer to fluorine, chlorine, bromine, and iodine.

[0040] The term "acyl group" refers to a substituted carbonyl group (-C(O)-R s ).

[0041] The term "ester" refers to a substituted oxycarbonyl group (-O-C(O)-R s or -C(O)-O-R s ).

[0042] The term "ether" refers to an -OR s group.

[0043] The terms "thio group" or "thioether" may be used interchangeably and refer to an -SR s group.

[0044] The term "selenoalkyl" refers to a -SeR s group.

[0045] The term "sulfinyl group" refers to a -S(O)-R s group.

[0046] The term "sulfonyl group" refers to a -SO2-R s group.

[0047] The term "phosphino group" refers to a group containing at least one phosphorus atom bonded to the relevant structure. Common examples of phosphino groups include, but are not limited to, groups such as -P(R s )2 group or -PO(R s )2 group, where each R s can be the same or different.

[0048] 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, groups such as -Si(R s)3 group, where each R s may be the same or different.

[0049] The term "germyl" refers to a group containing at least one germanium atom bonded to the relevant structure. Common examples of germyl groups include, but are not limited to, groups such as -Ge(R s )3 group, where each R s may be the same or different.

[0050] The term "boryl" refers to a group containing at least one boron atom bonded to the relevant structure. Common examples of boryl groups include, but are not limited to, groups such as -B(R s )2 group or its Lewis adduct -B(R s )3 group, where R s may be the same or different.

[0051] In each of the above, R s may be hydrogen or a substituent selected from the group consisting of general substituents as defined in this application. Preferred R s is selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, and combinations thereof. More preferably, R s is selected from the group consisting of: alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0052] The term "alkyl" refers to and includes both straight-chain and branched-chain alkyls having alkyl carbon atoms bonded to the relevant structure. Preferred alkyls are alkyls containing one to fifteen carbon atoms, preferably one to nine carbon atoms, and include methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, etc. Additionally, the alkyl may be further substituted.

[0053] The term "cycloalkyl" refers to and includes monocyclic, polycyclic, and spirocycloalkyls having cycloalkyl carbon atoms bonded to the relevant structure. Preferred cycloalkyls are cycloalkyls containing 3 to 12 ring carbon atoms and include cyclopropyl, cyclopentyl, cyclohexyl, bicyclo[3.1.1]heptyl, spiro[4.5]decyl, spiro[5.5]undecyl, adamantyl, etc. Additionally, the cycloalkyl may be further substituted.

[0054] The term "heteroalkyl" or "heterocycloalkyl" refers to an alkyl or cycloalkyl group having at least one carbon atom replaced by a heteroatom, respectively. Optionally, at least one heteroatom is selected from O, S, N, P, B, Si, Ge, and Se, preferably O, S, or N. Additionally, the heteroalkyl or heterocycloalkyl may be further substituted.

[0055] The term "alkenyl" refers to and includes both straight-chain and branched-chain olefin groups. An alkenyl is essentially an alkyl group that includes at least one carbon-carbon double bond in the alkyl chain, where one of the carbon atoms is from the carbon-carbon double bond bonded to the relevant structure. A cycloalkenyl is essentially a cycloalkyl group that includes at least one carbon-carbon double bond in the cycloalkyl ring. As used herein, the term "heteroalkenyl" refers to an alkenyl group having at least one carbon atom replaced by a heteroatom. Optionally, 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. Additionally, the alkenyl, cycloalkenyl, or heteroalkenyl may be further substituted.

[0056] The term "alkynyl" refers to and includes both straight-chain and branched-chain alkyne groups. An alkynyl is essentially an alkyl group that includes at least one carbon-carbon triple bond in the alkyl chain, where one of the carbon atoms is from the carbon-carbon triple bond bonded to the relevant structure. Preferred alkynyl groups are those containing two to fifteen carbon atoms. Additionally, the alkynyl may be further substituted.

[0057] The terms "aralkyl" or "arylalkyl" are used interchangeably and refer to an aryl-substituted alkyl group having alkyl carbon atoms bonded to the relevant structure. Additionally, the aralkyl may be further substituted.

[0058] The term "heterocyclic group" refers to and includes aromatic and non-aromatic ring groups containing at least one heteroatom. Optionally, at least one heteroatom is selected from O, S, Se, N, P, B, Si, Ge, and Se, preferably O, S, N, or B. A heteroaromatic ring group may be used interchangeably with a heteroaryl group. 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 morpholinyl, piperidinyl, pyrrolidinyl, etc., and cyclic ethers / sulfides such as tetrahydrofuran, tetrahydropyran, tetrahydrothiophene, etc. Additionally, the heterocyclic group may be further substituted or fused.

[0059] The term "aryl" means and includes both monocyclic and polycyclic aromatic hydrocarbon groups. The polycycle can have two or more rings, where 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, fluorene, phenanthrene, pyrene, perylene and azulene, preferably phenyl, biphenyl, terphenyl, triphenylene and naphthalene. Additionally, the aryl group can be further substituted or fused, such as but not limited to fluorene.

[0060] The term "heteroaryl" means and includes both monocyclic aromatic groups having at least one heteroatom and polycyclic aromatic ring systems. 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. The monocyclic heteroaromatic system is preferably a monocyclic ring having 5 or 6 ring atoms, and the ring can have one to six heteroatoms. The polycyclic heterocyclic system can have two or more aromatic rings, where two atoms are common to two adjacent rings (the rings are "fused"), where at least one of the rings is a heteroaryl. The polycyclic heteroaromatic ring system can have one to six heteroatoms in each ring of the polycyclic aromatic ring system. Preferred heteroaryl groups 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, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuranopyridine, furanodipyridine, benzothiophenopyridine, thiophenodipyridine, benzoselenophenopyridine, selenophenodipyridine, azaborine, borazine, 5λ 2 ,9λ 2 -diazab-13b-boraphenanthro[2,3,4-de]anthracene, 5λ 2-Benzo[d]benzo[4,5]imidazo[3,2-a]imidazole and 5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene; preferably dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 5λ 2 ,9λ 2 -diazaboranaphtho[2,3,4-de]anthracene, 5λ 2 -benzo[d]benzo[4,5]imidazo[3,2-a]imidazole and 5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene. Additionally, the heteroaryl may be further substituted or fused.

[0061] Among the aryl and heteroaryl listed above, triphenylene, naphthalene, anthracene, dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, pyrazine, pyrimidine, triazine, benzimidazole, 5λ 2 ,9λ 2 -diazaboranaphtho[2,3,4-de]anthracene, 5λ 2 -benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, 5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene groups, and their corresponding aza analogs are of particular interest.

[0062] In many cases, the general substituents are selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, selenyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

[0063] In some cases, the preferred general substituents are selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thio, and combinations thereof.

[0064] In some cases, the more preferred general substituents are selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, aryl, heteroaryl, nitrile, thio, and combinations thereof.

[0065] In some cases, the even more preferred general substituents are selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, silyl, aryl, heteroaryl, nitrile, and combinations thereof.

[0066] In other other cases, the most preferred general substituents are selected from the group consisting of deuterium, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0067] The terms "substituted" and "substitution" mean that a substituent other than H is bonded to the relevant position, such as carbon or nitrogen. For example, when R 1 represents monosubstitution, then one R 1 must not be H (i.e., substitution). Similarly, when R 1 represents disubstitution, then two R 1 must not be H. Similarly, when R 1 represents zero or no substitution, R 1 can be, for example, hydrogen at all available valences of the ring atoms, such as the carbon atoms of benzene and the nitrogen atom in pyrrole, or simply represent none for a ring atom with fully saturated valences, such as the nitrogen atom 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.

[0068] As used herein, "combinations thereof" means that one or more members of the applicable list are combined to form a known or chemically stable arrangement that a person of ordinary skill in the art can envision from the applicable list. For example, an alkyl and deuterium can be combined to form a partially or fully deuterated alkyl; a halogen and an alkyl can be combined to form a haloalkyl substituent; and a halogen, an alkyl, and an aryl can be combined to form a haloarylalkyl. In one example, the term substitution includes combinations of two to four of the listed groups. In another example, the term substitution includes combinations of two to three groups. In yet another example, the term substitution includes combinations of two groups. Preferred combinations of substituents are combinations containing up to fifty atoms that are not hydrogen or deuterium, or combinations including up to forty atoms that are not hydrogen or deuterium, or combinations including up to thirty atoms that are not hydrogen or deuterium. In many cases, the preferred combination of substituents will include up to twenty atoms that are not hydrogen or deuterium.

[0069] The "aza" name in the fragments described herein, such as aza-dibenzofuran, aza-dibenzothiophene, etc., means that one or more of the C-H groups in the corresponding aromatic ring can be replaced by a nitrogen atom. For example and without any limitation, aza-triphenylene encompasses dibenzo[f,h]quinoxaline and dibenzo[f,h]quinoline. Those of ordinary skill in the art can readily envision other nitrogen analogs of the aza-derivatives described above, and all such analogs are intended to be covered by the terms as set forth herein.

[0070] As used herein, "deuterium" refers to an isotope of hydrogen. Deuterated compounds can be readily prepared using methods known in the art. For example, U.S. Patent No. 8,557,400, Patent Publication No. WO 2006 / 095951, and U.S. Patent Application Publication No. US2011 / 0037057 (which are incorporated herein by reference in their entireties) describe the preparation of deuterium-substituted organometallic complexes. Further reference is made to Ming Yan et al., Tetrahedron 2015, 71, 1425-30 and Atzrodt et al., Angew. Chem. Int. Ed. (Review) 2007, 46, 7744-65 (which are incorporated by reference in their entireties) which respectively describe effective routes for the deuteration of methylene hydrogens in benzylamines and the replacement of aromatic ring hydrogens with deuterium.

[0071] As used herein, any specifically listed substituent, such as but not limited to methyl, phenyl, pyridyl, etc. includes its non-deuterated, partially deuterated, and fully deuterated forms. Similarly, substituents of classes such as but not limited to alkyl, aryl, cycloalkyl, heteroaryl, etc. also include their non-deuterated, partially deuterated, and fully deuterated forms. Unless otherwise specified, atoms in a chemical structure with valences not completely filled by H or D should be considered to include their non-deuterated, partially deuterated, and fully deuterated forms. For example, the chemical structure is meant to include C6H6, C6D6, C6H3D3, and any other of its partially deuterated variants. Some common substantially or fully deuterated groups include but are not limited to CD3, CD2C(CH3)3, C(CD3)3, and C6D5.

[0072] It should be understood that when a molecular fragment is described as a substituent or otherwise attached to another moiety, its name can be written as if it were a fragment (e.g., phenyl, phenylene, naphthyl, dibenzofuranyl) or as if it were the entire molecule (e.g., benzene, naphthalene, dibenzofuran). As used herein, these different ways of naming substituents or linking fragments are considered equivalent.

[0073] In some cases, a pair of substituents in a molecule can optionally be joined or fused to form a ring. Preferred rings are five- to nine-membered carbocyclic or heterocyclic rings, including cases where the portion of the ring formed by the pair of substituents is saturated and cases where the portion of the ring formed by the pair of substituents is unsaturated. In still other cases, a pair of adjacent substituents can optionally be joined or fused 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 adjacent rings having the two closest available substitutable positions (such as the 2,2'-positions in biphenyl or the 1,8-positions in naphthalene).

[0074] B. Compounds of the Present Disclosure

[0075] In one aspect, the present disclosure provides a compound having a first ligand L A wherein the first ligand L A comprises the structure of Formula I: wherein at least one of moiety B or moiety C has fused thereto the structure of Formula II In Formulas I and II:

[0076] Each of moiety A and moiety B is independently a 5- to 10-membered carbocyclic or heterocyclic ring;

[0077] Each of moiety D, moiety E, and (if present) moiety C is independently a monocyclic or polycyclic fused-ring system, wherein each ring of the monocyclic or polycyclic fused-ring system is independently a 5- to 10-membered carbocyclic or heterocyclic ring;

[0078] If moiety A is a 6-membered ring and moiety B is a 5-membered ring, then moiety C is present;

[0079] Z 1 to Z 6 each is independently C or N;

[0080] L 1 is selected from the group consisting of a direct 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';

[0081] Y is selected from the group consisting of 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';

[0082] K 1 and K 2 each is independently selected from the group consisting of a direct bond, O, S, N(R α ), P(R α ), B(R α ), C(R α )(R β ), and Si(R α )(R β );

[0083] R A , R B , R C , R D and R EEach of them independently represents mono-substitution to the maximum allowable substitution or no substitution;

[0084] Each R, R', R * , R α , R β , R A , R B , R C , R D and R E is independently hydrogen or a substituent selected from the group consisting of general substituents defined herein;

[0085] L A is coordinated with metal M;

[0086] Metal M has an atomic mass of at least 40 and can be coordinated with other ligands;

[0087] L A can be joined with other ligands to form a tridentate, tetradentate, pentadentate or hexadentate ligand; and

[0088] Any two substituents can be joined or fused to form a ring.

[0089] In some embodiments, the compound is not

[0090] In some embodiments, the compound comprises a first ligand L having the structure of Formula I A . In some embodiments, the compound comprises a first ligand L consisting essentially of Formula I A .

[0091] In some embodiments, at least one R A , R B , R C , R D or R E is selected from the group consisting of general substituents defined herein. In some embodiments, at least one R A is selected from the group consisting of general substituents defined herein. In some embodiments, at least one R B is selected from the group consisting of general substituents defined herein. In some embodiments, at least one R C is selected from the group consisting of general substituents defined herein. In some embodiments, at least one R D is selected from the group consisting of general substituents defined herein. In some embodiments, at least one R E is selected from the group consisting of general substituents defined herein.

[0092] In some embodiments of Formula I, R *, R A , R B , R C , R D or R E is partially or fully deuterated. In some embodiments, at least one R A is partially or fully deuterated. In some embodiments, at least one R B is partially or fully deuterated. In some embodiments, at least one R C is partially or fully deuterated. In some embodiments, at least one R D is partially or fully deuterated. In some embodiments, at least one R E is partially or fully deuterated. In some embodiments, R * is partially or fully deuterated. In some embodiments, at least one R or R' is partially or fully deuterated. In some embodiments, at least one R α or R β is partially or fully deuterated.

[0093] In some embodiments, each R, R', R * , R α , R β , R A , R B , R C , R D , and R E is independently hydrogen or a substituent selected from the group consisting of preferred general substituents as defined herein. In some embodiments, each R, R', R * , R α , R β , R A , R B , R C , R D , and R E is independently hydrogen or a substituent selected from the group consisting of more preferred general substituents as defined herein. In some embodiments, each R, R', R * , R α , R β , R A , R B , R C , R D , and R E is independently hydrogen or a substituent selected from the group consisting of most preferred general substituents as defined herein.

[0094] In some embodiments, two R D are fused to form a structure of Formula II.

[0095] In some embodiments, metal M is selected from the group consisting of Ir, Rh, Re, Ru, Os, Pt, Pd, Ag, Au, and Cu. In some embodiments, metal M is Ir. In some embodiments, metal M is Pt or Pd. In some embodiments, metal M is Pt. In some embodiments, metal M is Pd.

[0096] In some embodiments, each of moiety A and moiety B is independently a 5- or 6-membered carbocyclic or heterocyclic ring. In some embodiments, each of moiety A and moiety B is independently a 5- or 6-membered aryl or heteroaryl ring.

[0097] In some embodiments, each of moiety D, moiety E, and (if present) moiety C is independently a monocyclic or polycyclic fused ring system, wherein each ring of the monocyclic or polycyclic fused ring system is independently a 5- or 6-membered carbocyclic or heterocyclic ring. In some embodiments, each of moiety D, moiety E, and (if present) moiety C is independently a monocyclic or polycyclic fused ring system, wherein each ring of the monocyclic or polycyclic fused ring system is independently a 5- or 6-membered aryl or heteroaryl ring.

[0098] In some embodiments, each of moiety A and moiety B is independently selected from the group consisting of benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole, and triazole.

[0099] In some embodiments, moiety A is benzene, imidazole, or an imidazole-derived carbene.

[0100] In some embodiments, moiety B is benzene, imidazole, or furan.

[0101] In some embodiments, each of moiety D, moiety E, and (if present) moiety C is independently selected from the group consisting of 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, benzoselenophene, aza-benzoselenophene, indene, aza-indene, indole, aza-indole, benzimidazole, aza-benzimidazole, benzo-benzimidazole, aza-benzo-benzimidazole, carbazole, aza-carbazole, dibenzofuran, aza-dibenzofuran, dibenzothiophene, aza-dibenzothiophene, quinoxaline, phthalazine, phenanthrene, aza-phenanthrene, anthracene, aza-anthracene, phenanthridine, fluorene, and aza-fluorene. In some embodiments, the aza variants include one N located on a benzo ring. In some embodiments of moiety D, the aza variant includes one N on the benzo ring and the N is bonded to metal M.

[0102] In some embodiments, part D is a monocyclic ring. In some embodiments, part D is selected from the group consisting of: benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, imidazole-derived carbene, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole, and triazole. In some embodiments, part D is benzene, pyridine, or imidazole.

[0103] In some embodiments, part D is a polycyclic fused-ring system. In some embodiments, part D is selected from the group consisting of: naphthalene, quinoline, isoquinoline, quinazoline, benzofuran, aza-benzofuran, phenanthro[3,2-b]benzofuran, benzoxazole, aza-benzoxazole, benzothiophene, aza-benzothiophene, benzothiazole, aza-benzothiazole, benzoselenophene, aza-benzoselenophene, indene, aza-indene, indole, aza-indole, benzimidazole, benzimidazole-derived carbene, aza-benzimidazole, aza-benzimidazole-derived carbene, benzobenzimidazole, aza-benzobenzimidazole, carbazole, aza-carbazole, dibenzofuran, aza-dibenzofuran, dibenzothiophene, aza-dibenzothiophene, quinoxaline, phthalazine, phenanthrene, aza-phenanthrene, anthracene, aza-anthracene, phenanthridine, fluorene, and aza-fluorene. In some embodiments, part D is naphthalene, quinoline, isoquinoline, or benzimidazole.

[0104] In some embodiments, part D can be a polycyclic fused-ring structure. In some embodiments, part D can be a polycyclic fused-ring structure containing 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 metal M, and the second 6-membered ring is fused to the 5-membered ring. In some embodiments, part D is selected from the group consisting of: dibenzofuran, dibenzothiophene, dibenzoselenophene, and their aza-variants. In some such embodiments, part D can be further substituted at the ortho or meta position of the O, S, or Se atom with a substituent selected from the group consisting of: deuterium, fluorine, nitrile, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof. In some such embodiments, the aza-variant 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).

[0105] In some embodiments, part D can be a polycyclic fused-ring structure containing at least four fused rings. In some embodiments, the polycyclic fused-ring structure contains three 6-membered rings and one 5-membered ring. In some such embodiments, the 5-membered ring is fused to the ring coordinated to 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 the group consisting of: deuterium, fluorine, nitrile, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0106] In some embodiments, moiety D can be a polycyclic fused-ring structure comprising at least five fused rings. In some embodiments, the polycyclic 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 to a ring coordinated to metal M, a second 6-membered ring is fused to the 5-membered ring, a third 6-membered ring is fused to the second 6-membered ring, and a fourth 6-membered ring is fused to the third 6-membered ring.

[0107] In some embodiments, moiety D can be the aza form of the polycyclic fused-ring described above. In some such embodiments, moiety D can contain exactly one aza N atom. In some such embodiments, moiety D can contain exactly two aza N atoms, which can be in one ring or in two different rings. In some such embodiments, the ring having the aza N atom is separated from the metal M atom by at least two other rings. In some such embodiments, the ring having the aza N atom is separated from the metal M atom by at least three other rings. In some such embodiments, each of the ortho positions of the aza N atom is substituted.

[0108] In some embodiments, moiety E is a monocyclic ring. In some embodiments, moiety E is selected from the group consisting of benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole, and triazole. In some embodiments, moiety E is benzene.

[0109] In some embodiments, moiety E is a polycyclic fused-ring system. In some embodiments, moiety E is selected from the group consisting of naphthalene, quinoline, isoquinoline, quinazoline, benzofuran, aza-benzofuran, benzoxazole, aza-benzoxazole, benzothiophene, aza-benzothiophene, benzothiazole, aza-benzothiazole, benzoselenophene, aza-benzoselenophene, indene, aza-indene, indole, aza-indole, benzimidazole, aza-benzimidazole, carbazole, aza-carbazole, dibenzofuran, aza-dibenzofuran, dibenzothiophene, aza-dibenzothiophene, quinoxaline, phthalazine, phenanthrene, aza-phenanthrene, anthracene, aza-anthracene, phenanthridine, fluorene, and aza-fluorene. In some embodiments, moiety E is naphthalene or benzofuran.

[0110] In some embodiments, moiety C is absent.

[0111] In some embodiments, moiety C is present. In some embodiments, moiety A is a 5-membered ring, moiety B is a 6-membered ring, or both.

[0112] In some embodiments, part C is a single ring. In some embodiments, part C is selected from the group consisting of: benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole, and triazole. In some embodiments, part C is benzene.

[0113] In some embodiments, part C is a polycyclic fused ring system. In some embodiments, part C is selected from the group consisting of: naphthalene, quinoline, isoquinoline, quinazoline, benzofuran, aza-benzofuran, benzoxazole, aza-benzoxazole, benzothiophene, aza-benzothiophene, benzothiazole, aza-benzothiazole, benzoselenophene, aza-benzoselenophene, indene, aza-indene, indole, aza-indole, benzimidazole, aza-benzimidazole, carbazole, aza-carbazole, dibenzofuran, aza-dibenzofuran, dibenzothiophene, aza-dibenzothiophene, quinoxaline, phthalazine, phenanthrene, aza-phenanthrene, anthracene, aza-anthracene, phenanthridine, fluorene, and aza-fluorene. In some embodiments, part C is naphthalene.

[0114] In some embodiments, Z 1 is C and Z 4 is N or a carbene carbon. In some embodiments, Z 4 is N. In some embodiments, Z 4 is a carbene carbon.

[0115] In some embodiments, Z 1 is N or a carbene carbon, and Z 4 is C. Z 1 is N. In some embodiments, Z 1 is a carbene carbon.

[0116] In some embodiments, Z 2 and Z 3 are both C.

[0117] In some embodiments, Z 2 is C and Z 3 is N. In some such embodiments, Z 4 is a carbene carbon.

[0118] In some embodiments, Z 2 is N and Z 3 is C. In some such embodiments, Z 1 is a carbene carbon.

[0119] In some embodiments, Z 5 and Z 6 are C. In some embodiments, at least one of Z 5 or Z 6 is N. In some embodiments, Z 5 is N. In some embodiments, Z6 is N.

[0120] In some embodiments, K 1 is a direct bond.

[0121] In some embodiments, K 1 is O or S. In some embodiments, K 1 is O. In some embodiments, K 1 is S. In some embodiments, K 1 is N(R α ), P(R α ), or B(R α ). In some embodiments, K 1 is C(R α )(R β ), or Si(R α )(R β ).

[0122] In some embodiments, K 2 is a direct bond.

[0123] In some embodiments, K 2 is O or S. In some embodiments, K 2 is O. In some embodiments, K 2 is S. In some embodiments, K 2 is N(R α ), P(R α ), or B(R α ). In some embodiments, K 2 is C(R α )(R β ), or Si(R α )(R β ).

[0124] In some embodiments, each of K 1 and K 2 is a direct bond.

[0125] In some embodiments, K 1 is a direct bond, and K 2 is not a direct bond. In some embodiments, K 2 is a direct bond, and K 1 is not a direct bond.

[0126] In some embodiments, Y is selected from the group consisting of O, S, and Se.

[0127] In some embodiments, Y is selected from the group consisting of BR, NR, and PR. In some embodiments, Y is BR. In some embodiments, Y is NR. In some embodiments, Y is PR. In some of the foregoing embodiments, R is aryl or heteroaryl. In some such embodiments, R is aryl or heteroaryl and is joined or fused with R E , R B or R C to form a fused ring.

[0128] In some embodiments, Y is selected from the group consisting of P(O)R, C═O, C═S, C═Se, C═NR', C═CRR', S═O, and SO2. In some embodiments, BRR', CRR', SiRR', and GeRR'. In some embodiments, Y is CR.

[0129] In some embodiments, L 1 is selected from the group consisting of O, S, and Se.

[0130] In some embodiments, L 1 is selected from the group consisting of CR, BR, NR, and PR. In some embodiments, L 1 is Br. In some embodiments, L 1 is NR. In some embodiments, L 1 is PR. In some embodiments, R is aryl or heteroaryl. In some such embodiments, R is aryl or heteroaryl and is joined or fused with R B , R C or R D to form a fused ring.

[0131] In some embodiments, L 1 is selected from the group consisting of P(O)R, C═O, C═S, C═Se, C═NR', C═CRR', S═O, and SO2. In some embodiments, L 1 is selected from the group consisting of BRR', CRR', SiRR', and GeRR'.

[0132] In some embodiments, L 1 is a direct bond.

[0133] In some embodiments, the structure of Formula II is fused with moiety B. In some such embodiments, moiety C is absent. In other embodiments, moiety C is present.

[0134] In some embodiments, the structure of Formula II is fused with moiety C.

[0135] In some embodiments, the compound comprises a moiety selected from the group consisting of:

[0136]

[0137] Wherein:

[0138] X is independently C or N each time it appears;

[0139] Y A is selected from the group consisting of: BR, BRR', NR, PR, P(O)R, O, S, Se, C═O, C═S, C═Se, C═NR, C═CRR', S═O, SO2, CRR', SiRR' and GeRR';

[0140] Y G is independently selected from the group consisting of: 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' each time it appears;

[0141] is a single bond or a double bond, provided that two adjacent bonds are not both double bonds at the same time;

[0142] Each R W is independently halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, seleno or a combination thereof;

[0143] The remaining variables are the same as those previously defined; and

[0144] Any two substituents may optionally be fused or joined to form a ring.

[0145] It should be understood that each X in a single ring in each of the above structures may be the same or different. In some embodiments, all Xs in the structure are carbon. In some embodiments, at least one X in a structure is N. In some embodiments, in a structure, at most four Xs may independently be N. In some such embodiments, each N is in a different ring. In some embodiments, at most two Ns may be in a single ring of the structure.

[0146] 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 Hammett constant of the electron-withdrawing group is 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.

[0147] In some embodiments, Formula I includes an electron-withdrawing group selected from the group consisting of 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 k2 , substituted or unsubstituted dibenzoborolene, 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, cyanoalkyl, cyanoaryl, cyanoheteroaryl, isocyanate,

[0148]

[0149] where each R k1 represents mono-substitution to the maximum allowable substitution, or no substitution;

[0150] where Y G is selected from the group consisting of: 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' ; and

[0151] where R k1 , R k2 , R k3 , R e and R fEach of which is independently hydrogen or a substituent selected from the group consisting of general substituents as defined herein.

[0152] In some embodiments, Formula I comprises an electron-withdrawing group selected from the group consisting of structures in the following EWG2 list:

[0153]

[0154]

[0155] In some embodiments, Formula I comprises an electron-withdrawing group selected from the group consisting of structures in the following EWG3 list:

[0156] In some embodiments, Formula I comprises an electron-withdrawing group selected from the group consisting of structures in the following EWG4 list:

[0157]

[0158] In some embodiments, Formula I comprises an electron-withdrawing group, and the electron-withdrawing group is a π-deficient electron-withdrawing group. In some embodiments, the π-deficient electron-withdrawing group is selected from the group consisting of: 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 k1 )3, Br k1 R k2 , substituted or unsubstituted dibenzoborolene, 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,

[0159] wherein said variables are the same as those defined previously.

[0160] In some embodiments, the compound comprises an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, the compound comprises an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, the compound comprises an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, the compound comprises an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, the compound comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0161] In some embodiments, at least one R A is or comprises an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R A is or comprises an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R A is or comprises an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R A is or comprises an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R A is or comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0162] In some embodiments, at least one R B is or comprises an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R B is or comprises an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R B is or comprises an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R B is or comprises an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R B is or comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0163] In some embodiments, at least one R C is or comprises an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R C is or comprises an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R C is or comprises an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one RC is or comprises an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R C is or comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0164] In some embodiments, at least one R D is or comprises an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R D is or comprises an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R D is or comprises an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R D is or comprises an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R D is or comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0165] In some embodiments, at least one R E is or comprises an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R E is or comprises an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R E is or comprises an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R E is or comprises an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R E is or comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0166] In some embodiments, R * is or comprises an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, R * is or comprises an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, R * is or comprises an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, R * is or comprises an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, R * is or comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0167] In some embodiments, L AContains an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, L A Contains an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, L A Contains an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, L A Contains an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, L A Contains an electron-withdrawing group from the Pi-EWG list as defined herein.

[0168] In some embodiments, R * Is not hydrogen.

[0169] In some embodiments, R * Contains at least one C atom. In some embodiments, R * Contains substituents selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0170] In some embodiments, R * Is joined or fused to R E To form ring E1. In some such embodiments, Formula II is fused to ring B. In some such embodiments, Formula II is fused to ring C. In some embodiments, ring E1 is a 5- or 6-membered carbocyclic or heterocyclic ring.

[0171] In some embodiments, ring E1 is a 6-membered ring. In some embodiments, ring E1 is a 5-membered ring.

[0172] In some embodiments, ring E1 is not aromatic. In some embodiments, ring E1 contains at least one N or O atom.

[0173] In some embodiments, the structure of Formula II is fused to moiety C, and R * Is joined or fused to R C To form ring C1. In some embodiments, ring C1 is a 5- or 6-membered carbocyclic or heterocyclic ring.

[0174] In some embodiments, ring C1 is not aromatic. In some embodiments, ring C1 contains at least one N, B, or O atom.

[0175] In some embodiments, the structure of Formula II is fused to moiety B, and R * Is joined or fused to R B To form ring B1. In some embodiments, ring B1 is a 5- or 6-membered carbocyclic or heterocyclic ring.

[0176] In some embodiments, ring B1 is not aromatic. In some embodiments, ring B1 contains at least one N, B, or O atom.

[0177] In some embodiments, at least one of the Rs A is not hydrogen. In some embodiments, at least one R A contains at least one C atom. In some embodiments, at least one R A contains substituents selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0178] In some embodiments, at least one of the Rs B is not hydrogen. In some embodiments, at least one R B contains at least one C atom. In some embodiments, at least one R B contains substituents selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0179] In some embodiments, two Rs B are joined or fused to form a 5- or 6-membered heterocyclic or carbocyclic ring.

[0180] In some embodiments, at least one of the Rs C is not hydrogen. In some embodiments, at least one R C contains at least one C atom. In some embodiments, at least one R C contains substituents selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0181] In some embodiments, two Rs C are joined or fused to form a 5- or 6-membered heterocyclic or carbocyclic ring.

[0182] In some embodiments, at least one of the Rs D is not hydrogen. In some embodiments, at least one R D contains at least one C atom. In some embodiments, at least one R D contains substituents selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0183] In some embodiments, at least one of the Rs E is not hydrogen. In some embodiments, at least one R E contains at least one C atom. In some embodiments, at least one R E contains substituents selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0184] In some embodiments, Formula II may be selected from the group consisting of the structures of the following list W1:

[0185]

[0186] Wherein:

[0187] X is independently CR or N each time it appears;

[0188] Y A is selected from the group consisting of: 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';

[0189] Y G is independently selected from the group consisting of: 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' each time it appears;

[0190] is a single bond or a double bond;

[0191] Each R W is independently a halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, germyl, boranyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, seleno or a combination thereof;

[0192] The remaining variables are the same as those previously defined;

[0193] Any two substituents may optionally be joined fused or joined to form a ring; and

[0194] The wavy line is fused to part B or part C of formula I.

[0195] In some embodiments, ligand L A is selected from the group consisting of the structures of List 1A below:

[0196]

[0197]

[0198]

[0199]

[0200]

[0201] Wherein:

[0202] Y1 To Y 22 Each of which is independently selected from the group consisting of C and N;

[0203] Each of Y' and Y” is selected from the group consisting of: BR e 、BR e R f 、NR e 、PR e 、P(O)R e 、O, S, Se, C═O, C═S, C═Se, C═NR e 、C═CR e R f 、S═O, SO2, CR e R f 、SiR e R f and GeR e R f ;

[0204] T is selected from the group consisting of: B, Al, Ga, and In;

[0205] K 1 and K 2 Each of which is selected from the group consisting of: a single bond, O, S, NR e 、PR e 、BR e 、CR e R f and SiR e R f ;

[0206] R e and R f may be fused or joined to form a ring;

[0207] Each R A 、R B 、R C 、R D and R G independently represents mono-substituted to the maximum allowable number of substitutions, or no substitution;

[0208] R A 、R B 、R C 、R D 、R G 、R N 、R M 、R T 、R e and R f Each of which is independently hydrogen or a substituent selected from the group of general substituents defined herein;

[0209] The remaining variables are the same as those defined previously;

[0210] R A 、R B 、R C 、R D 、R G 、R N 、R M and R T any two adjacent substituents of and R can be fused or joined to form a ring or form a polydentate ligand; and

[0211] The structure of Formula II is fused to Part B or Part C.

[0212] In some embodiments, the structure from List W1 is fused to Part B of the structure from List 1A. In some embodiments, the structure from List W1 is fused to Part C of the structure from List 1A.

[0213] In some embodiments, the ligand L A has the following structure:

[0214] Wherein:

[0215] Z A1 、Z A2 、Z A3 and Z A4 and X are each independently C or N each time it appears;

[0216] The dashed bond represents a single bond or a double bond, but two adjacent dashed bonds are not both double bonds at the same time;

[0217] Y A1 、Y A2 、Y A3 and Y A4 each independently selected from the group consisting of: no 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';

[0218] When present, Y A4 is bonded to another ligand;

[0219] k is a linking group selected from: 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', and n is an integer selected from 0 to 2;

[0220] R AB , R AC and R AD Each of the above independently represents mono-substitution to the maximum permissible substitution, or no substitution;

[0221] Each R, R', R AB , R AC and R AD are independently hydrogen or a substituent selected from the group consisting of general substituents defined herein; and

[0222] Any two substituents may be optionally joined or fused to form a ring.

[0223] In some embodiments, the ligand L A Selected from the group consisting of the following structures of Listing 1:

[0224]

[0225]

[0226]

[0227]

[0228]

[0229]

[0230]

[0231]

[0232]

[0233]

[0234] in:

[0235] For each occurrence, each X, Z A1 , Z A2 , Z A3 and Z A4 are independently C or N;

[0236] k is a linker selected from 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', and n is an integer selected from 0 to 2;

[0237] Y A1 , Y A2 , YA3 and Y A4 Each of which is independently selected from the group consisting of: no 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';

[0238] There is at least one Y A1 、Y A2 、Y A3 or Y A4 ;

[0239] When present, Y A4 binds to another ligand;

[0240] R AB 、R AC and R AD Each of which independently represents mono-substitution to the maximum allowable substitution, or no substitution;

[0241] Each R, R', R AB 、R AC and R AD is independently hydrogen or a substituent selected from the group of general substituents defined herein; and

[0242] Any two substituents may be joined or fused to form a ring.

[0243] It should also be understood that each X in a single ring may be the same or different. In some embodiments, all Xs in the structure are carbon. In some embodiments, at least one X in the structure is N. In some embodiments, at most four Xs in the structure may independently be N. In some such embodiments, each N is in a different ring. In some embodiments, at most two Ns may be in a single ring of the structure.

[0244] In some embodiments where the ligand L A is selected from List 1, at least one R AB 、R AC or R AD is selected from the group of general substituents defined herein. In some embodiments, at least one R AB is selected from the group of general substituents defined herein. In some embodiments, at least one R AC is selected from the group of general substituents defined herein. In some embodiments, at least one R AD is selected from the group of general substituents defined herein.

[0245] In some embodiments where the ligand L A is selected from List 1, RAB , R AC or R AD is at least partially or fully deuterated. In some embodiments, at least one R AB is at least partially or fully deuterated. In some embodiments, at least one R AC is at least partially or fully deuterated. In some embodiments, at least one R AD is at least partially or fully deuterated. In some embodiments, at least one R or R' is at least partially or fully deuterated.

[0246] In some embodiments where the ligand L A is selected from List 1, at least one R AB is or comprises an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R AB is or comprises an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R AB is or comprises an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R AB is or comprises an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R AB is or comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0247] In some embodiments where the ligand L A is selected from List 1, at least one R AC is or comprises an electron-withdrawing group from the EWG1 list as defined herein. In ligand L A is selected from List 1, at least one R AC is or comprises an electron-withdrawing group from the EWG2 list as defined herein. In ligand L A is selected from List 1, at least one R AC is or comprises an electron-withdrawing group from the EWG3 list as defined herein. In ligand L A is selected from List 1, at least one R AC is or comprises an electron-withdrawing group from the EWG4 list as defined herein. In ligand L A is selected from List 1, at least one R AC is or comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0248] In some embodiments where the ligand L A is selected from List 1, at least one R ADis or comprises an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R AD is or comprises an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R AD is or comprises an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R AD is or comprises an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R AD is or comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0249] In some embodiments, ligand L A is selected from the group consisting of the structures of List 2A below:

[0250]

[0251]

[0252]

[0253]

[0254]

[0255]

[0256]

[0257]

[0258]

[0259]

[0260]

[0261]

[0262]

[0263] wherein:

[0264] Y 2 、Y 6 and Y 14 each independently is selected from the group consisting of C and N;

[0265] Each of Y' and Y” is independently selected from the group consisting of: BR e 、BR e R f 、NR e 、PR e 、P(O)R e 、O, S, Se, C=O, C=S, C=Se, C=NR e 、C=CR e R f 、S=O, SO2, CR e R f 、SiR e R f and GeR e R f ;

[0266] T is selected from the group consisting of: B, Al, Ga and In;

[0267] K 1 and K 2 each is selected from the group consisting of: a single bond, O, S, NR e 、PR e 、BR e 、CR e R f and SiR e R f ;

[0268] R e and R f may be fused or joined to form a ring;

[0269] Each R A 、R B 、R C 、R D and R G independently represents mono-substitution to the maximum allowable number of substitutions, or no substitution;

[0270] R A 、R B 、R C 、R D 、R G 、R N 、R M 、R T 、R e and R f each is independently hydrogen or a substituent selected from the group of general substituents defined herein;

[0271] R A 、R B 、R C 、RD , R G , R N , R M and R T Any two adjacent substituents of and R may be fused or joined to form a ring or form a polydentate ligand; and

[0272] Formula II is fused to ring B, ring C, ring C1, ring C2 or ring C3 of the structures in the above list.

[0273] In some embodiments, the structure from List W1 is fused to ring B of the structure from List 2A. In some embodiments, the structure from List W1 is fused to ring C of the structure from List 2A. In some embodiments, the structure from List W1 is fused to ring C1 of the structure from List 2A. In some embodiments, the structure from List W1 is fused to ring C2 of the structure from List 2A. In some embodiments, the structure from List W1 is fused to ring C3 of the structure from List 2A.

[0274] In some embodiments, ligand L A is selected from the group consisting of the structures of List 2 below:

[0275]

[0276]

[0277]

[0278]

[0279]

[0280]

[0281]

[0282]

[0283]

[0284]

[0285]

[0286]

[0287]

[0288]

[0289]

[0290]

[0291]

[0292] Wherein:

[0293] R AB 、R AC 、R AD 、R AE and R AF each independently represents mono-substitution to the maximum allowable substitution, or no substitution;

[0294] Each R AB 、R AC 、R AD 、R AE and R AF is independently hydrogen or a substituent selected from the group consisting of general substituents defined herein; and

[0295] Any two substituents may be joined or fused to form a ring.

[0296] In some embodiments, for example, two Rs associated with the imidazole or pyridine ring in the above structure AD may be linked together to form a benzene or naphthalene ring fused to the associated imidazole or pyridine ring.

[0297] In some embodiments where the ligand L A is selected from List 2, at least one R AB 、R AC 、R AD 、R AE or R AF is selected from the group consisting of general substituents defined herein. In some embodiments, at least one R AB is selected from the group consisting of general substituents defined herein. In some embodiments, at least one R AC is selected from the group consisting of general substituents defined herein. In some embodiments, at least one R AD is selected from the group consisting of general substituents defined herein. In some embodiments, at least one R AE is selected from the group consisting of general substituents defined herein. In some embodiments, at least one R AF is selected from the group consisting of general substituents defined herein.

[0298] In some embodiments where the ligand L A is selected from List 2, R AB 、R AC 、RAD , R AE or R AF at least one of which is partially or fully deuterated. In some embodiments, at least one R AB is partially or fully deuterated. In some embodiments, at least one R AC is partially or fully deuterated. In some embodiments, at least one R AD is partially or fully deuterated. In some embodiments, at least one R AE is partially or fully deuterated. In some embodiments, at least one R AF is partially or fully deuterated.

[0299] In some embodiments where the ligand L A is selected from List 2, at least one R AB is or comprises an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R AB is or comprises an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R AB is or comprises an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R AB is or comprises an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R AB is or comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0300] In some embodiments where the ligand L A is selected from List 2, at least one R AC is or comprises an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments where the ligand L A is selected from List 1, at least one R AC is or comprises an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments where the ligand L A is selected from List 1, at least one R AC is or comprises an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments where the ligand L A is selected from List 1, at least one R AC is or comprises an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments where the ligand L A is selected from List 1, at least one R AC is or comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0301] In some embodiments where the ligand L AIn some embodiments selected from List 2, at least one R AD is or comprises an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R AD is or comprises an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R AD is or comprises an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R AD is or comprises an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R AD is or comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0302] In ligand L A In some embodiments selected from List 2, at least one R AE is or comprises an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R AE is or comprises an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R AE is or comprises an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R AE is or comprises an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R AE is or comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0303] In ligand L A In some embodiments selected from List 2, at least one R AF is or comprises an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R AF is or comprises an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R AF is or comprises an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R AF is or comprises an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R AF is or comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0304] In some embodiments, ligand L A is selected from L Ai-(Ri)(Rj)(Rk)(Rl), where i is an integer from 1 to 79; and each of Ri, Rj, Rk, and Rl is independently selected from the group consisting of R1 to R468, and L A 1-(R1)(R1)(R1)(R1) to L A Each of 79-(R468)(R468)(R468)(R468) is defined in List 3 below:

[0305]

[0306]

[0307]

[0308]

[0309]

[0310]

[0311]

[0312]

[0313]

[0314]

[0315] Where R1 to R468 have the structures defined in List 4 below:

[0316]

[0317]

[0318]

[0319]

[0320]

[0321]

[0322]

[0323]

[0324]

[0325]

[0326]

[0327]

[0328]

[0329]

[0330]

[0331]

[0332]

[0333]

[0334]

[0335]

[0336]

[0337] In some embodiments, the compound has the formula M(L A ) p (L B ) q (L C ) r , where L B and L C are each a bidentate ligand; and where 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 the metal M.

[0338] In some embodiments, the compound has a formula selected from the group consisting of: 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 ); and where L A , L B , and L C are different from each other.

[0339] In some embodiments, L B comprises an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, L BContains an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, L B Contains an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, L B Contains an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, L B Contains an electron-withdrawing group from the Pi-EWG list as defined herein.

[0340] In some embodiments, L C Contains an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, L C Contains an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, L C Contains an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, L C Contains an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, L C Contains an electron-withdrawing group from the Pi-EWG list as defined herein.

[0341] In some embodiments, L B Is a substituted or unsubstituted phenylpyridine, and L C Is a substituted or unsubstituted acetylacetonate.

[0342] In some embodiments, the compound has the formula Pt(L A )(L B ); and wherein L A and L B can be the same or different. In some embodiments, L A and L B are linked to form a tetradentate ligand.

[0343] In some embodiments, L B and L C are each independently selected from the group consisting of the structures of List 5 below:

[0344]

[0345]

[0346]

[0347] Wherein:

[0348] T is selected from the group consisting of: B, Al, Ga, and In;

[0349] K 1'Selected from the group consisting of: a single bond, O, S, NR e , PR e , BR e , CR e R f and SiR e R f ;

[0350] Y 1 to Y 13 each independently selected from the group consisting of C and N;

[0351] Y' is selected from the group consisting of: BR e , BR e R f , NR e , PR e , P(O)R e , O, S, Se, C═O, C═S, C═Se, C═NR e , C═CR e R f , S═O, SO2, CR e R f , SiR e R f and GeR e R f ;

[0352] R e and R f may be fused or joined to form a ring;

[0353] each R a , R b , R c and R d independently represents mono-substitution to the maximum allowable number of substitutions, or no substitution;

[0354] R a1 , R b1 , R c1 , R d1 , R a , R b , R c , R d , R e and R f each independently is hydrogen or a substituent selected from the group of general substituents defined herein; and

[0355] R a1 , R b1 , R c1 , R d1 , R a , Rb , R c and R d Any two adjacent substituents of and may be fused or joined to form a ring or form a polydentate ligand.

[0356] In some embodiments, L B and L C are each independently selected from the group consisting of the structures of Listing 6 below:

[0357]

[0358]

[0359]

[0360]

[0361]

[0362]

[0363] Wherein:

[0364] R a ', R b ', R c ', R d ', and R e ' each independently represent zero, single, or up to the maximum allowable number of substitutions on their respective rings;

[0365] R a ', R b ', R c ', R d ', and R e ' are each independently hydrogen or a substituent selected from the group of general substituents defined herein; and

[0366] R a ', R b ', R c ', R d ', and R e ' of two substituents may be fused or joined to form a ring or form a polydentate ligand.

[0367] In some embodiments, L B comprises of the structure, where the variables are the same as previously defined. In some embodiments, each of Y 1 to Y 4 is independently carbon. In some embodiments, each of Y 1 to Y 4At least one of them is N. In some embodiments, Y 1 to Y 4 Exactly one of them is N. In some embodiments, Y 1 is N. In some embodiments, Y 2 is N. In some embodiments, Y 3 is N. In some embodiments, Y 4 is N. In some embodiments, at least one R a is a tertiary alkyl group, a silyl group or a germyl group. In some embodiments, R a At least one of them is a tertiary alkyl group. In some embodiments, Y 3 is C, and the R a connected to it is a tertiary alkyl group, a silyl group or a germyl group. In some embodiments, Y 1 to Y 3 are C, Y 4 is N, and the R 3 connected to Y a is a tertiary alkyl group, a silyl group or a germyl group. In some embodiments, Y 1 to Y 3 are C, Y 4 is N, and the R 2 connected to Y a is a tertiary alkyl group, a silyl group or a germyl group. In some embodiments, at least one R b is a tertiary alkyl group, a silyl group or a germyl group. In some embodiments, the tertiary alkyl group is a tert-butyl group. In some embodiments, at least one pair of R a , a pair of R b or a pair of R a and R b join or condense to form a ring.

[0368] In some embodiments, the compound has the formula Ir(L A )3, the formula Ir(L A )(L Bk )2, the formula Ir(L A )2(L Bk ), the formula Ir(L A )2(L Cj-I ) or Ir(L A )2(L Cj-II ),

[0369] where L A is according to any of the embodiments described herein, including L A 1-(R1)(R1)(R1)(R1) to L A 47-(R468)(R468)(R468)(R468);

[0370] where k is an integer from 1 to 836, and each L Bk has the structure defined in Listing 7 below:

[0371]

[0372]

[0373]

[0374]

[0375]

[0376]

[0377]

[0378]

[0379]

[0380]

[0381]

[0382]

[0383]

[0384]

[0385]

[0386]

[0387]

[0388]

[0389]

[0390]

[0391]

[0392]

[0393]

[0394]

[0395]

[0396]

[0397]

[0398]

[0399]

[0400]

[0401]

[0402]

[0403]

[0404]

[0405]

[0406]

[0407] Each L Cj-I has a structure based on the formula ;

[0408] Each L Cj-II has a structure based on the formula where for each L Cj-I and L Cj-II among L Cj , R 201 and R 202 are defined in the following list:

[0409]

[0410]

[0411]

[0412]

[0413]

[0414]

[0415]

[0416]

[0417]

[0418]

[0419]

[0420] wherein R D1 to R D246 has the structure in List 9 below:

[0421]

[0422]

[0423]

[0424] In some embodiments, the compound is selected from the group consisting of compounds corresponding to only one of the following: L Bk , L B1 , L B2 , L B18 , L B28 , L B38 , L B108 , L B118 , L B122 , L B124 , L B126 , L B128 , L B130 , L B132 , L B134 , L B136 , L B138 , L B140 , L B142 , L B144 , L B156 , L B158 , L B160 , L B162 , L B164 , L B168 , L B172 , L B175 , L B204 , L B206 , L B214 , L B216 , L B218 , L B220 , L B222 , L B231 , L B233 , L B235 , L B237 , LB240 , L B242 , L B244 , L B246 , L B248 , L B250 , L B252 , L B254 , L B256 , L B258 , L B260 , L B262 , L B264 , L B265 , L B266 , L B267 , L B268 , L B269 and L B270 .

[0425] In some embodiments, the compound is selected from the group consisting of compounds having only L Bk corresponding to one of the following: L B1 , L B2 , L B18 , L B28 , L B38 , L B108 , L B118 , L B122 , L B126 , L B128 , L B132 , L B136 , L B138 , L B142 , L B156 , L B162 , L B204 , L B206 , L B214 , L B216 , L B218 , L B220 , L B231 , L B233 , L B 237 , L B264 , L B265 , L B266 , L B267 , L B268 , L B269 and L B270 .

[0426] In some embodiments, the compound is selected from the group consisting of compounds having only those L 201 and R 202 defined as one of the following structures: L Cj-I or L Cj-II ligands: R D1 , R D3 , RD4 , 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 .

[0427] In some embodiments, the compound is selected from the group consisting of only those compounds having an L 201 and an R 202 defined as an L Cj-I or an L Cj-II ligand 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 an R D246 .

[0428] In some embodiments, the compound is selected from the group consisting of only those compounds having one of the following structures of the L Cj-I ligand in the following List 10:

[0429]

[0430] In some embodiments, the compound has a chemical formula selected from the group consisting of: Ir(L A )3, Ir(L A )2(LB ), Ir(L A )(L B )2, Ir(L A )2(L C ) and Ir(L A )(L B )(L C ). In some embodiments, L A is selected from the group consisting of the structures of List 1, List 1A, List 2, List 2A, and List 3, L B is selected from the group consisting of the structures of List 5, List 6, and List 7(L Bk ), and L C is selected from the group consisting of the L Cj-I and L Cj-II defined in List 7.

[0431] In some embodiments, L A is selected from the group consisting of the structure of List 1, and L B is selected from the group consisting of the structure of L Bk . In some embodiments, L A is selected from the group consisting of the structures in List 1A, and L B is selected from the group consisting of the structure of L Bk . In some embodiments, L A is selected from the group consisting of the structures of List 2, and L B is selected from the group consisting of the structure of L Bk . In some embodiments, L A is selected from the group consisting of the structures of List 2A, and L B is selected from the group consisting of the structure of L Bk . In some embodiments, L A is selected from List 3 as defined herein, and L B is selected from the group consisting of the structure of L Bk , where k is an integer from 1 to 836. In some embodiments, L A is selected from List 1 as defined herein, and L C is selected from the group consisting of the structure of L Cj-I and L Cj-II , where j is an integer from 1 to 1416.

[0432] In some embodiments, the compound may have the formula Ir(L A i-(Ri)(Rj)(Rk)(Rl))3, the formula Ir(L A i-(Ri)(Rj)(Rk)(Rl))(L B )2, the formula Ir(L Ai-(Ri)(Rj)(Rk)(Rl))2(L B )), formula Ir(L A )(L Bk )2, formula Ir(L A )2(L Bk ), from Ir(L A 1-(R1)(R1)(R1)(R1))(L B1 )2 to Ir(L A 79-(R468)(R468)(R468)(R468))(L B836 )2 of the compounds consisting of formula Ir(L A i-(Ri)(Rj)(Rk)(Rl))(L Bk )2, from the compound Ir(L A 1-(R1)(R1)(R1)(R1))2(L B1 ) to Ir(L A 79-(R468)(R468)(R468)(R468))2(L B836 ) consisting of formula Ir(L A i-(Ri)(Rj)(Rk)(Rl))2(L Bk ), from the compound Ir(L A 1-(R1)(R1)(R1)(R1))2(L C1-I ) to Ir(L A 79-(R468)(R468)(R468)(R468))2(L C1416-I ) consisting of formula Ir(L A i-(Ri)(Rj)(Rk)(Rl))2(L Cj-I ), from the compound Ir(L A 1-(R1)(R1)(R1)(R1))2(L C1-II ) to Ir(L A 79-(R468)(R468)(R468)(R468))2(L C1416-II ) consisting of formula Ir(L A i-(Ri)(Rj)(Rk)(Rl))2(L Cj-II ), from the compound Ir(L A 1-(R1)(R1)(R1)(R1))(L B1 )(L C1-I ) to Ir(L A 79-(R468)(R468)(R468)(R468))(L B836 )(L C1416-I ) consisting of formula Ir(L Ai-(Ri)(Rj)(Rk)(Rl))(L Bk )(L Cj-I ) or a compound Ir(L A 1-(R1)(R1)(R1)(R1))(L B1 )(L C1-II ) to Ir(L A 79-(R468)(R468)(R468)(R468))(L B836 )(L C1416-II ) consisting of the formula Ir(L A i-(Ri)(Rj)(Rk)(Rl))(L Bk )(L Cj-II ), where L A i-(Ri)(Rj)(Rk)(Rl), L Bk and L Cj-I and L Cj-II are all as defined herein.]

[0433] In some embodiments, the compound is selected from the group consisting of the structures of List 11 below:

[0434]

[0435]

[0436]

[0437]

[0438]

[0439]

[0440]

[0441]

[0442] In some embodiments, the compound has the formula III:

[0443] Wherein:

[0444] M 1 is Pd or Pt;

[0445] Moieties E' and F' are each independently a monocyclic or polycyclic structure comprising a 5- to 10-membered carbocyclic or heterocyclic ring;

[0446] Z 3* and Z 4* are each independently C or N;

[0447] K 1 、K 2 、K 3 and K 4 are each independently selected from the group consisting of a direct bond, O, and S, where at least two of them are direct bonds;

[0448] L 1 、L 2 and L 3 are each independently absent or selected from the group consisting of: a direct bond, BR, BRR', NR, PR, P(O)R, O, S, Se, C═O, C═S, C═Se, C═NR, C═CRR', S═O, SO2, CRR', SiRR', GeRR', alkylene, cycloalkyl, aryl, subcycloalkyl, subaryl, heteroaryl, and combinations thereof, where at least one of L 1 and L 2 is present;

[0449] R E' and R F' each independently represent zero, one, or up to the maximum allowable number of substitutions on their respective rings;

[0450] R, R', R E' and R F' each independently is hydrogen or a substituent selected from the group of general substituents defined herein; and

[0451] when chemically feasible, two adjacent Rs A 、R B 、R C 、R E 、R E' and R F' can be joined or fused together to form a ring.

[0452] In some embodiments, each of R, R', R E' and R F' is independently hydrogen or a substituent selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, boranyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thio, and combinations thereof.

[0453] In some embodiments, portions E' and F' are each independently a monocyclic or polycyclic structure comprising a 5 - or 6 - membered carbocyclic or heterocyclic ring.

[0454] In some embodiments of Formula III, at least one R A is selected from the group of general substituents defined herein. In some embodiments, at least one RB is selected from the group consisting of general substituents as defined herein. In some embodiments, at least one R C is selected from the group consisting of general substituents as defined herein. In some embodiments, at least one R D is selected from the group consisting of general substituents as defined herein. In some embodiments, at least one R E' is selected from the group consisting of general substituents as defined herein. In some embodiments, at least one R F' is selected from the group consisting of general substituents as defined herein.

[0455] In some embodiments of Formula III, at least one of R, R', R A , R B , R C , R D , R E , R E' or R F' is partially or fully deuterated. In some embodiments, at least one R A is partially or fully deuterated. In some embodiments, at least one R B is partially or fully deuterated. In some embodiments, at least one R C is partially or fully deuterated. In some embodiments, at least one R D is partially or fully deuterated. In some embodiments, at least one R E is partially or fully deuterated. In some embodiments, at least one R E' is partially or fully deuterated. In some embodiments, at least one R F' is partially or fully deuterated. In some embodiments of Formula II, at least R or R' is present and is partially or fully deuterated.

[0456] In some embodiments of Formula III, at least one of R, R', R A , R B , R C , R D , R E , R E' or R F' is or comprises an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one of R, R', R A , R B , R C , R D , R E , R E' or R F'is or comprises an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one of R, R', R A , R B , R C , R D , R E , R E' or R F' is or comprises an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one of R, R', R A , R B , R C , R D , R E , R E' or R F' is or comprises an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one of R, R', R A , R B , R C , R D , R E , R E' or R F' is or comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0457] In some embodiments of Formula III, at least one R A is or comprises an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R A is or comprises an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R A is or comprises an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R A is or comprises an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R A is or comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0458] In some embodiments of Formula III, at least one R B is or comprises an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R B is or comprises an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R B is or comprises an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R Bis or comprises an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R B is or comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0459] In some embodiments of Formula III, at least one R C is or comprises an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R C is or comprises an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R c is or comprises an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R C is or comprises an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R C is or comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0460] In some embodiments of Formula III, at least one R D is or comprises an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R D is or comprises an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R D is or comprises an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R D is or comprises an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R D is or comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0461] In some embodiments of Formula III, at least one R E is or comprises an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R E is or comprises an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R E is or comprises an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R E is or comprises an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R E is or comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0462] In some embodiments of Formula III, at least one R E' is or comprises an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R E' is or comprises an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R E' is or comprises an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R E' is or comprises an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R E' is or comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0463] In some embodiments of Formula III, at least one R F' is or comprises an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R F' is or comprises an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R F' is or comprises an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R F' is or comprises an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R F' is or comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0464] In some embodiments, Formula III comprises an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, Formula III comprises an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, Formula III comprises an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, Formula III comprises an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, Formula III comprises an electron-withdrawing group from the Pi-EWG list as defined herein.]

[0465] In some embodiments of Formula III, both moiety E' and moiety F' are 6-membered aromatic rings.

[0466] In some embodiments of Formula III, moiety F' is a 5-membered or 6-membered heteroaromatic ring.

[0467] In some embodiments of Formula III, L 1 is O or CRR'.

[0468] In some embodiments of Formula III, Z 4 is N and Z3 is C. In some embodiments of Formula III, Z 4 is C and Z 3 is N.

[0469] In some embodiments of Formula III, L 2 is a direct bond. In some embodiments of Formula III, L 2 is NR.

[0470] In some embodiments of Formula III, K 1 , K 2 , K 3 and K 4 are all direct bonds. In some embodiments of Formula III, one of K 1 , K 2 , K 3 and K 4 is O.

[0471] In some embodiments of Formula III, the compound is selected from the group consisting of compounds having the formula Pt(L A' )(Ly):

[0472]

[0473] wherein L A' is selected from the group consisting of the structures of List 12 below:

[0474]

[0475]

[0476] wherein L y is selected from the group consisting of the structures of List 13 below:

[0477]

[0478] wherein:

[0479] For each occurrence, each X, Z A1 , Z A2 , Z A3 and Z A4 is independently C or N;

[0480] X A3 is selected from the group consisting of: 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';

[0481] Y A1 , Y A2 , Y A3 and Y A4 each of which is independently selected from the group consisting of: absence of a 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';

[0482] There is at least one Y A1 , Y A2 , Y A3 or Y A4 ;

[0483] When present, Y A4 Bond to another ligand;

[0484] R AB , R AC , R AD , R EE and R EF Each of the above independently represents a single substitution to the maximum permissible substitution, or no substitution;

[0485] Each R, R', R AB , R AC , R AD , R EE and R EF are independently hydrogen or a substituent selected from the group consisting of general substituents defined herein; and

[0486] Any two substituents may be optionally joined or fused to form a ring.

[0487] In some embodiments, R, R', R AB , R AC , R AD , R EE and R EF Each of is independently selected from the group consisting of R1 to R468 defined in List 4 defined herein.

[0488] In some embodiments, the compound is selected from the group consisting of compounds having the formula Pt(L A' The group consisting of compounds of )(Ly):

[0489]

[0490] Where L A' Selected from L A'i'-(Lw)(Rm)(Rn)(Ro)(Rp), where i' is an integer from 1 to 63; Lw can be L1 or L2, where Lw is a direct bond for L1 and Lw is -O- for L2; and each of Rm, Rn, Ro, and Rp is independently selected from the group consisting of R1 to R468, and L A' 1-(L1)(R1)(R1)(R1)(R1) to L A' 63-(L2)(R468)(R468)(R468)(R468) is defined in the following Listing 14:

[0491]

[0492]

[0493]

[0494]

[0495]

[0496]

[0497]

[0498] where L y is selected from L y w-(Rs)(Rt)(Ru), where w is an integer from 1 to 48; and each of Rs, Rt, and Ru is independently selected from the group consisting of R1 to R468, and L y 1-(R1)(R1)(R1) to L y 48-(R468)(R468)(R468) is defined in the following Listing 15:

[0499]

[0500]

[0501]

[0502]

[0503] where each of R1 to R468 has the structure defined in Listing 4 as defined herein.

[0504] In some embodiments, the compound is selected from the group consisting of the structures of the following Listing 16:

[0505]

[0506] In some embodiments, the first ligand L of formula I described herein A The 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 ordinary meaning and includes the percentage of all possible hydrogen atoms (e.g., positions of hydrogen or deuterium) occupied by deuterium atoms in the compound. In some embodiments, the carbon atoms constituting the ring coordinated to the metal M are fully or partially deuterated. In some embodiments, the carbon atoms contained in the polycyclic system coordinated to the metal M are fully or partially deuterated. In some embodiments, the substituents attached to the monocyclic or fused polycyclic system coordinated to the metal M are fully or partially deuterated.

[0507] In some embodiments, the emission of the compound of formula I at room temperature has 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.

[0508] In some embodiments of the heteroleptic compound of formula M(L A ) p (L B ) q (L C ) r the ligand L A has a first substituent R I , where the first atom a-I in the first substituent R I is the farthest from the metal M among all the atoms of the ligand L A . Additionally, the ligand L B (if present) has a second substituent R II , where the first atom a-II in the second substituent R II is the farthest from the metal M among all the atoms of the ligand L B . Further, the ligand L C (if present) has a third substituent R III , where the first atom a-III in the third substituent R III is the farthest from the metal M among all the atoms of the ligand L C .

[0509] In such heteroleptic compounds, the vectors V D1 , V D2 and V D3 can be defined as follows. V D1 represents the direction from the metal M to the first atom a-I, and the vector VD1 The value D 1 represents the straight-line distance between the metal M and the first atom a-I in the first substituent R I . V D2 represents the direction from the metal M to the first atom a-II, and the vector V D2 The value D 2 represents the straight-line distance between the metal M and the first atom a-II in the second substituent R II . V D3 represents the direction from the metal M to the first atom a-III, and the vector V D3 The value D 3 represents the straight-line distance between the metal M and the first atom a-III in the third substituent R III .

[0510] In such heteroleptic compounds, a sphere with a radius r is defined, the center of which is the metal M and the radius r is the minimum radius that allows the sphere to enclose all the atoms that are not part of the substituents R I , R II and R III ; and wherein D 1 , D 2 and D 3 is at least one of which is at least larger than the radius r by In some embodiments, D 1 , D 2 and D 3 is at least one of which is at least larger than the radius r by 2.9, 3.0, 4.3, 4.4, 5.2, 5.9, 7.3, 8.8, 10.3, 13.1, 17.6 or In some embodiments, D 1 , D 2 and D 3 is at least two of which are at least larger than the radius r by 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

[0511] In some embodiments of such heteroleptic compounds, the compound has a transition dipole moment axis, and the angles between the transition dipole moment axis and the vectors V D1 , V D2 and V D3 are determined, wherein the transition dipole moment axis and the vectors V D1 , V D2 and V D3 at least one of the angles between is less than 40°. In some embodiments, the transition dipole moment axis and the vectors V D1 , V D2 and V D3At least one of the angles between is less than 30°, 20°, 15°, or 10°. In some embodiments, the transition dipole moment axis and the vector V D1 , V D2 and V D3 At least two of the angles between are less than 20°. In some embodiments, the transition dipole moment axis and the vector V D1 , V D2 and V D3 At least two of the angles between are less than 15° or 10°.

[0512] In some embodiments, the transition dipole moment axis and the vector V D1 , V D2 and V D3 All three of the angles between are less than 20°. In some embodiments, the transition dipole moment axis and the vector V D1 , V D2 and V D3 All three of the angles between are less than 15° or 10°.

[0513] In some embodiments of such heteroleptic compounds, the compound has a vertical dipole ratio (VDR) of 0.33 or less. In some embodiments of such heteroleptic compounds, the compound has a VDR of 0.30, 0.25, 0.20, or 0.15 or less.

[0514] One of ordinary skill in the art will readily understand the meaning of the terms transition dipole moment axis of a compound and vertical dipole ratio of a compound. However, the meaning of these terms can be found in U.S. Patent No. 10,672,997, the disclosure of which is incorporated herein by reference in its entirety. In U.S. Patent No. 10,672,997, the horizontal dipole ratio (HDR) of a compound is discussed rather than the VDR. However, one of ordinary skill in the art will readily understand that VDR = 1 - HDR.

[0515] In some embodiments, the compound can be an emissive dopant. In some embodiments, the compound can produce emission via phosphorescence, fluorescence, thermally activated delayed fluorescence, triplet-triplet annihilation, or a combination of these methods. In some embodiments, the emissive dopant can be a racemic mixture or can be enriched in one enantiomer. In some embodiments, the compounds of the present invention can have different stereoisomers, such as fac and mer. The present compounds relate to individual isomers and mixtures of various isomers in any mixing ratio. In some embodiments, the compound can be homoleptic (each ligand is the same). In some embodiments, the compound can be heteroleptic (at least one ligand is different from the others). In some embodiments, when there is more than one ligand coordinated to the metal, the ligands can all be the same. In some other embodiments, at least one ligand is different from the other ligands. In some embodiments, each ligand can be different from all the other ligands. This also holds in embodiments where the ligands coordinated to the metal can be linked to other ligands coordinated to the metal to form tridentate, tetradentate, pentadentate, or hexadentate ligands. Thus, in cases where the coordinated ligands are linked together, in some embodiments, all the ligands can be the same, and in some other embodiments, at least one of the linked ligands can be different from the other ligands.

[0516] In yet another aspect of the present disclosure, a formulation comprising a novel compound disclosed herein is described. The formulation can include one or more components selected from the group consisting of solvents, emitters, hosts, hole injection materials, hole transport materials, electron blocking materials, hole blocking materials, and electron transport materials disclosed herein.

[0517] The present disclosure encompasses any chemical structure that includes the novel compounds of the present disclosure or their monovalent or multivalent variants. In other words, the inventive compounds or their monovalent or multivalent variants can be part of a larger chemical structure. Such chemical structures can be selected from the group consisting of: monomers, polymers, macromolecules, and supramolecules (also referred to as supermolecules). As used herein, a "monovalent variant of a compound" refers to the same moiety as the compound, but where one hydrogen has been removed and replaced with a bond that attaches to the remainder of the chemical structure. As used herein, a "multivalent variant of a compound" refers to the same moiety as the compound, but where more than one hydrogen has been removed and replaced with one or more bonds that attach to the remainder of the chemical structure. In the case of a supramolecule, the inventive compounds can also be incorporated into the supramolecular complex without a covalent bond. As used in this context, the description that structure A contains moiety B means that structure A includes the structure of moiety B, and the structure of moiety B does not include the H or D atoms that can be attached to moiety B. This is because at least one H or D on a given moiety structure must be replaced with a substituent such that moiety B can be part of structure A, and after it becomes part of structure A, one or more of the H or D on the given moiety B structure can be further substituted.

[0518] C. OLEDs and Devices of the Present Disclosure

[0519] In another aspect, the present disclosure also provides an OLED device that includes a first organic layer containing a compound as disclosed in the above compound moieties of the present disclosure.

[0520] In some embodiments, the OLED includes: an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer includes a first ligand L having a structure of Formula I as defined herein A of a compound.

[0521] 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 can be an emissive layer and the compound as described herein can be an emissive dopant or a non-emissive dopant.

[0522] In some embodiments, the organic layer can further include a host, wherein the host includes at least one chemical group selected from the group consisting of: triphenylene, carbazole, indolocarbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, 5λ 2-Benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, 5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene, azacyclohexaborane, oxaborole, dihydroacridine, xanthene, dihydrobenzoazasiline, dibenzooxasiline, phenoxazine, phenoxathiin, phenothiazine, dihydrophenazine, fluorene, naphthalene, anthracene, phenanthrene, phenanthroline, benzoquinoline, quinoline, isoquinoline, quinazoline, pyrimidine, pyrazine, pyridine, triazine, boranyl, silyl, aza-triphenylene, aza-carbazole, aza-indolocarbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, aza-5λ 2 -Benzo[d]benzo[4,5]imidazo[3,2-a]imidazole and aza-(5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene).

[0523] In some embodiments, the host may be selected from the group consisting of the structures in Host Group 1 below:

[0524]

[0525]

[0526]

[0527]

[0528]

[0529]

[0530]

[0531]

[0532]

[0533] Wherein:

[0534] Each of J1 to J6 is independently C or N;

[0535] L' is a direct bond or an organic linking group;

[0536] Each Y AA 、Y BB 、Y CC and Y DD is independently selected from the group consisting of: no bond, direct bond, O, S, Se, CRR', SiRR', GeRR', NR, BR, BRR';

[0537] R A' 、R B' 、R C' 、R D' 、R E' 、R F' and R G' each independently represents mono - substitution, up to maximum substitution or no substitution;

[0538] each R, R', R A' 、R B' 、R C' 、R D' 、R E' 、R F' and R G' is independently hydrogen or a substituent selected from the group consisting of general substituents as defined herein; any two substituents may be joined or fused to form a ring; and

[0539] where possible, each unsubstituted aromatic carbon atom is optionally replaced by N to form a nitrogen - substituted ring.

[0540] 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 is independently O, S or SiRR', or more preferably O or S. In some embodiments, at least one unsubstituted aromatic carbon atom is replaced by N to form a nitrogen - containing ring.

[0541] In some embodiments, the host 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:

[0542]

[0543]

[0544] The structures of MG1 to MG27 are shown below:

[0545] In the MGb structure shown above, two bonding positions in the asymmetric structures MG10, MG11, MG12, MG13, MG14, MG17, MG24, and MG25 are marked with numbers for identification purposes.

[0546] In some embodiments, the host may be any one of its N-heterosubstituted variants, its fully or partially deuterated variants, and combinations thereof. In some embodiments, the host has the formula EGa-MGb-Egc and is selected from the group consisting of h1 to h112 defined in the following host group 2 list, where each of MGb, EGa, and Egc is defined as follows:

[0547]

[0548]

[0549] 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 labeled with a numerical prefix that identifies their bonding position in the MGb structure.

[0550] In some embodiments, the organic layer may further comprise a host, wherein the host comprises a metal complex.

[0551] In some embodiments, the emissive layer may comprise two hosts: a first host and a second host. In some embodiments, the first host is a hole-transporting host and the second host is an electron-transporting host. In some embodiments, the first host is a hole-transporting host and the second host is a bipolar host. In some embodiments, the first host is an electron-transporting host and the second host is a bipolar host. In some embodiments, the first host and the second host may form an exciplex. In some embodiments, the emissive layer may comprise a third host. In some embodiments, the third host is selected from the group consisting of: an insulating host (wide-bandgap host), a hole-transporting host, and an electron-transporting host. In some embodiments, the third host forms an exciplex with one of the first host and the second host or with both the first host and the second host. In some embodiments, the emissive layer may comprise a fourth host. In some embodiments, the fourth host is selected from the group consisting of: an insulating host (wide-bandgap host), a hole-transporting host, and an electron-transporting host. In some embodiments, the fourth host forms an exciplex with one of the first host, the second host, and the third host, with two of the first host, the second host, and the third host, or with each of the first host, the second host, and the third host. In some embodiments, the LUMO of the electron-transporting 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-transporting host is higher than -5.6 eV, higher than -5.5 eV, higher than -5.4 eV, or higher than -5.35 eV. The HOMO and LUMO values can be determined electrochemically in solution. Cyclic voltammetry and differential pulse voltammetry in solution can be performed using a CH Instruments model 6201B potentiostat, using anhydrous dimethylformamide (DMF) solvent and tetrabutylammonium hexafluorophosphate as a supporting electrolyte. Glassy carbon, platinum wire, and silver wire are used as the working electrode, counter electrode, and reference electrode, respectively. By measuring the peak potential difference by differential pulse voltammetry, the electrochemical potential can be referenced to the internal ferrocene-ferrocenium redox couple (Fc / Fc+).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 R.F., Bassler H., Porsch M., Daub, J. Adv. Mater. 1995, 7, 551), the corresponding highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energies are determined by referring the cationic and anionic redox potentials to ferrocene (4.8 eV vs. vacuum).

[0552] In some embodiments, the compounds as described herein can be a sensitizer or a component of a sensitizer; wherein the device can further comprise an acceptor that receives energy from the sensitizer. In some embodiments, the acceptor is an emitter in the device. In some embodiments, the acceptor can be a fluorescent material. In some embodiments, the compounds as described herein can be used as a phosphorescent sensitizer in an OLED, wherein one or more layers in the OLED contain an acceptor in the form of one or more non - delayed fluorescence and / or delayed fluorescence materials. In some embodiments, the compounds as described herein can be used as a component of an exciplex that acts as a sensitizer. As a phosphorescent sensitizer, the compound must be able to transfer energy to the acceptor and the acceptor will emit energy or further transfer the energy to a final emitter. The acceptor concentration can range from 0.001% to 99.9%. The acceptor can be in the same layer as the phosphorescent sensitizer or in one or more different layers. In some embodiments, the acceptor is a thermally activated delayed fluorescence (TADF) material. In some embodiments, the acceptor is a non - delayed fluorescence material. In some embodiments, the emission can be generated by any one or all of the sensitizer, acceptor, and final emitter. In some embodiments, the emission of the acceptor at room temperature has 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.

[0553] As used herein, phosphorescence generally refers to photon emission when there is a change in the electron spin quantum number, i.e., the initial and final states of the emission have different electron spin quantum numbers, such as from the T1 to the S0 state. Most of the Ir and Pt complexes currently used in OLEDs are phosphorescent emitters. In some embodiments, if the exciplex formation involves a triplet emitter, such exciplexes can also emit phosphorescence. On the other hand, a fluorescent emitter generally refers to photon emission when the electron spin quantum number remains unchanged, such as from the S1 to the S0 state, or from the D1 to the D0 state. A fluorescent emitter can be a delayed fluorescence or non-delayed fluorescence emitter. Depending on the spin state, a fluorescent emitter can be a singlet emitter or a doublet emitter or other multiplet 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, namely 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 rely on the collision of two triplets, but rather on the thermal population between the triplet and the singlet excited state. Thermal energy can activate the triplet transition back to the singlet. This type of delayed fluorescence is also referred to as TADF. E-type delayed fluorescence characteristics can be seen in exciplex systems or single compounds. Without being bound by theory, it is believed that TADF emission requires a compound or exciplex with a small singlet-triplet energy gap (ΔE S-T ) less than or equal to 400, 350, 300, 250, 200, 150, 100, or 50 meV. There are two main types of TADF emitters, one called donor-acceptor type TADF and the other called multi-resonant (MR) TADF. Generally, 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). A donor-acceptor exciplex can be formed between a hole transporting compound and an electron transporting compound. Examples of MR-TADF materials include highly conjugated fused ring systems. In some embodiments, the MR-TADF materials contain boron, carbon, and nitrogen atoms. Such materials can also contain other atoms, such as oxygen. In some embodiments, the reverse intersystem crossing time from T1 to S1 for delayed fluorescence emission at 293K is less than or equal to 10 microseconds. In some embodiments, such time can be greater than 10 microseconds and less than 100 microseconds.

[0554] In some embodiments, the OLED can comprise additional compounds selected from the group consisting of: non-delayed fluorescent materials, delayed fluorescent materials, phosphorescent materials, and combinations thereof.

[0555] In some embodiments, the inventive compounds described herein are phosphorescent materials.

[0556] 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 energy 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 a receptor. In some embodiments, the phosphorescent material forms an exciplex with another material (e.g., a host material, an emitter material) within the OLED.

[0557] 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 energy 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 a receptor, and the OLED further includes a sensitizer.

[0558] In some embodiments of the OLED, the delayed fluorescent material includes at least one donor group and at least one acceptor group. In some embodiments, the delayed fluorescent material is a metal complex. In some embodiments, the delayed fluorescent material is a non-metal complex. In some embodiments, the delayed fluorescent 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 fluorescent material includes a metal-carbene bond. In some embodiments, the non-delayed fluorescent material or the delayed fluorescent material includes at least one chemical group selected from the group consisting of: aryl-amine, aryloxy, arylthio, triphenylene, carbazole, indolocarbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, 5λ 2 -benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, 5,9-dioxa-13b-boraperylene[3,2,1-de]anthracene, 5λ 2 ,9λ 2 -diazaborylene[2,3,4-de]anthracene, 5-oxa-9λ 2-aza-13b-boraphenanthro[3,2,1-de]anthracene, azaborinane, oxaborole, dihydroacridine, xanthene, dihydrobenzazasilole, dibenzooxasilole, phenoxazine, phenoxathiin, phenothiazine, dihydro-phenazine, fluorene, naphthalene, anthracene, phenanthrene, phenanthroline, benzoquinoline, quinoline, isoquinoline, quinazoline, pyrimidine, pyrazine, pyridine, triazine, boranyl, amino, silyl, their aza-variants, and combinations thereof. In some embodiments, the non-delayed fluorescent material or the delayed fluorescent material comprises tris(aryl / heteroaryl)borane, wherein one or more pairs of substituents from the aryl / heteroaryl are joined to form a ring. In some embodiments, the fluorescent material comprises at least one chemical group selected from the group consisting of naphthalene, anthracene, fluoranthene, phenanthrene, fluorene, pyrene, perylene, and azulene.

[0559] In yet another aspect, the OLEDs of the present disclosure may further comprise an emissive region containing a compound or a formulation of compounds as disclosed in the above compound portions of the present disclosure. In some embodiments, the emissive region may comprise a compound or a formulation of compounds having a first ligand L having the structure of Formula I defined herein A . In some embodiments, the emissive region consists of one or more organic layers, wherein at least one of the one or more organic layers has a minimum thickness selected from the group consisting of 350, 400, 450, 500, 550, 600, 650, and In some embodiments, at least one of the one or more organic layers is formed of an emissive 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 can be obtained in U.S. Patent Application Publication No. 2023 / 0292605, the entire content of which is incorporated herein by reference. In some embodiments, at least one of the one or more organic layers comprises a compound or a formulation of compounds as disclosed in Part A and Part D of the present disclosure.

[0560] In some embodiments, the OLEDs or emissive regions containing the compounds of the present invention disclosed herein can be incorporated into a full-color pixel arrangement of a device. The full-color pixel arrangement of such a device includes at least one pixel, wherein the at least one pixel includes a first sub-pixel and a second sub-pixel. The first sub-pixel includes a first OLED that contains a first emissive region. The second sub-pixel includes a second OLED that contains a second emissive region. In some embodiments, the first and / or second OLEDs, the first and / or second emissive regions can be the same or different and each can independently have various device features and various embodiments of the compounds of the present invention included therein, as well as various combinations and sub-combinations of various device features and various embodiments of the compounds of the present invention included therein, as disclosed herein.

[0561] In some embodiments, the first emissive region is configured to emit light having a peak wavelength λ max1 ; the second emissive region is configured to emit light having a peak wavelength λ max2 . In some embodiments, the difference between the peak wavelength λ max1 and λ max2 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 emissive region is configured to emit light having a peak wavelength λ max1 in a region of the visible spectrum of 400 - 500 nm, 500 - 600 nm, 600 - 700 nm; and the second emissive region is configured to emit light having a peak wavelength λ max2 in one of the remaining regions of the visible spectrum of 400 - 500 nm, 500 - 600 nm, 600 - 700 nm. In some embodiments, the first emissive region contains (if more than one) a first number of emissive layers deposited one on top of the other; and the second emissive region contains (if more than one) a second number of emissive layers deposited one on top of the other; and the first number is different from the second number. In some embodiments, both the first emissive region and the second emissive region contain phosphorescent materials that can be the same or different. In some embodiments, the first emissive region contains a phosphorescent material while the second emissive region contains a fluorescent material. In some embodiments, both the first emissive region and the second emissive region contain fluorescent materials that can be the same or different.

[0562] In some embodiments, at least one pixel of the OLED or emissive region includes 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 emissive region; and wherein the total number of emissive regions within at least one pixel is equal to or less than N-1. In some embodiments, the second emissive region is identical to the first emissive region; and each sub-pixel of at least one pixel includes one emissive region identical to the first emissive region. In some embodiments, the full-color pixel arrangement may have a plurality of pixels including a first pixel region and a second pixel region; wherein at least one display characteristic of the first pixel region is different from the corresponding display characteristic of the second pixel region, and wherein at least one display characteristic is selected from the group consisting of: resolution, cavity mode, color, out-coupling, and color filter.

[0563] In some embodiments, the OLED is a stacked OLED including one or more charge generation layers (CGLs). In some embodiments, the OLED includes a first electrode, a first emissive region disposed above the first electrode, a first CGL disposed above the first emissive region, a second emissive region disposed above the first CGL, and a second electrode disposed above the second emissive region. In some embodiments, the first emissive region and / or the second emissive region may have various device characteristics as described above for the pixelated device. In some embodiments, the stacked OLED is configured to emit white. In some embodiments, one or more of the emissive regions in the pixelated OLED or the stacked OLED include a sensitizer and a receptor having various sensitization device characteristics and various embodiments of the inventive compounds disclosed herein. For example, the first emissive region is included in the sensitization device while the second emissive region is not included in the sensitization device; in some cases, both the first emissive region and the second emissive region are included in the sensitization device.

[0564] In some embodiments, the OLED can emit light from the plasmon mode with at least 1%, 5%, 10%, 30%, 50%, 70%, 80%, 90%, 95%, 99% or 100% of the light. In some embodiments, at least one of the anode, the cathode, or a new layer disposed above the organic emission layer serves as an enhancement layer. The enhancement layer includes a plasmonic material that exhibits surface plasmon resonance, the plasmonic material is non-radiatively coupled to the emitter material, and transfers the excited state energy from the emitter material to the non-radiative mode of the surface plasmon polariton. In some embodiments, the enhancement layer is disposed at a distance not exceeding a threshold distance from the organic emission layer, where due to the presence of the enhancement layer, the emitter material has a total non-radiative decay rate constant and a total radiative decay rate constant. The threshold distance is the position where the total non-radiative decay rate constant is equal to 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 non-radiative decay rate constant and the total radiative decay rate constant is equal to the photoluminescence yield of the emitter material in the absence of the enhancement layer.

[0565] In some embodiments, the OLED further includes an out-coupling layer. In some embodiments, the out-coupling layer is disposed on the side opposite to the organic emission layer above the enhancement layer. The out-coupling layer scatters the energy from the surface plasmon polariton. In some embodiments, this energy is scattered as photons into free space. In other embodiments, the energy is scattered from the surface plasmon mode of the device into other modes, such as but not limited to organic waveguide mode, substrate mode, or another waveguide mode. In some embodiments, one or more intermediate layers can be disposed between the enhancement layer and the out-coupling layer. Examples of the intermediate layer can be dielectric materials, including organic, inorganic, perovskite, oxides, and can include stacks and / or mixtures of these materials.

[0566] The enhancement layer changes the effective properties of the medium in which the emitter material resides, thereby causing any one or all of the following: reduced emissivity, changed emission line shape, angular variation of emission intensity, changed emitter material stability, changed OLED efficiency, and reduced roll-off efficiency of the OLED device. Placing the enhancement layer on the cathode side, the anode side, or both sides, or placing the enhancement layer itself as a CGL produces an OLED device that utilizes any of the above effects. In addition to the specific functional layers described in the various OLED examples mentioned herein and shown in the figures, the OLED according to the present disclosure may further include any other functional layers common in OLEDs.

[0567] In some embodiments, the enhancement layer may comprise a plasmonic material, an optically active metamaterial, or a hyperbolic metamaterial. In some embodiments, the plasmonic material includes at least one metal. In such embodiments, the metal may include 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 enhancement layer is provided as a planar layer. In other embodiments, the enhancement layer has features of wavelength size arranged periodically, quasi-periodically, or randomly, or features of sub-wavelength size arranged periodically, quasi-periodically, or randomly.

[0568] In some embodiments, the outer coupling layer has features of wavelength size or sub-wavelength size 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 above 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 the enhancement layer, or changing the material of the enhancement layer. The plurality of nanoparticles of the device can be formed by 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, where 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 lithography.

[0569] In some embodiments of the plasmonic device, the emitter and / or host compound used in the emission 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.

[0570] In yet another aspect, the present disclosure also provides a consumer product that includes an organic light emitting device (OLED) having an anode; a cathode; and an organic layer disposed between the anode and the cathode, where the organic layer may include a compound or formulation of compounds as disclosed in the above compound portion of the present disclosure.

[0571] 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, where the organic layer can include a first ligand L having a structure of Formula I as defined herein A of a compound.

[0572] Generally, an OLED includes at least one organic layer disposed between and electrically connected to an anode and a cathode. When a current is applied, the anode injects holes and the cathode injects electrons into the organic layer. The injected holes and electrons each migrate toward the oppositely charged electrode. When an electron and a hole are located on the same molecule, an “exciton” is formed, which is a localized electron-hole pair having an excited energy state. When the exciton relaxes through a light-emission mechanism, light is emitted. In some cases, the exciton can be localized as an excimer or an exciplex. Non-radiative mechanisms, such as thermal relaxation, can also occur but are generally considered undesirable.

[0573] Figure 1 An organic light-emitting device 100 is shown. The figure is not necessarily drawn to scale. Device 100 can 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 barrier layer 170. Cathode 160 is a composite cathode having a first conductive layer 162 and a second conductive layer 164. Device 100 can be fabricated by depositing the layers in sequence. The properties and functions of these various layers and example materials are described in more detail in columns 6-10 of US 7,279,704, which is incorporated by reference.

[0574] Additional instances of each of these layers can be obtained. For example, 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 molar ratio of 50:1, as disclosed in U.S. Patent Application Publication No. 2003 / 0230980, which is incorporated herein by reference in its entirety. Examples of the light-emitting 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 molar ratio of 1:1, as disclosed in U.S. Patent Application Publication No. 2003 / 0230980, which disclosure is incorporated herein by reference in its entirety. U.S. Patent Nos. 5,703,436 and 5,707,745, which are incorporated herein by reference in their entireties, disclose examples of cathodes that include a composite cathode having a thin layer of metal (such as Mg:Ag) with an overlying transparent, conductive, sputter-deposited ITO layer. The theory and use of the barrier layer 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 entireties. Examples of the injection layer are provided in U.S. Patent Application Publication No. 2004 / 0174116, which is incorporated herein by reference in its entirety. A description of the protective layer can be found in U.S. Patent Application Publication No. 2004 / 0174116, which is incorporated herein by reference in its entirety.

[0575] Figure 2 An inverted OLED 200 is shown. The device includes a substrate 210, a cathode 215, an emissive layer 220, a hole transport layer 225, and an anode 230. The device 200 can be fabricated by depositing the layers in sequence. Since the most common OLED configuration has a cathode disposed above the anode, and the device 200 has a cathode 215 disposed under the anode 230, the device 200 can be referred to as an "inverted" OLED. Materials similar to those described with respect to the device 100 can be used in the corresponding layers of the device 200. Figure 2 An example is provided of how some of the layers can be omitted from the structure of the device 100.

[0576] Figure 1 and 2The simple layer structure described herein is provided by way of non-limiting example, and it should be understood that embodiments of the present disclosure may 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 may be used. Functional OLEDs may be obtained by combining the various layers described in different ways, or the layers may 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 of the examples provided herein describe the various layers as including a single material, it should be understood that combinations of materials may be used, such as a mixture of a host and a dopant, or more generally, mixtures. Additionally, the layers may have various sub-layers. 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 emissive layer 220, and may 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 multiple layers of different organic materials such as, for example, as described with respect to Figure 1 and 2 The multiple layers of different organic materials.

[0577] Structures and materials not specifically described may also be used, such as an OLED (PLED) comprising a polymeric material, as disclosed, for example, in U.S. Patent No. 5,247,190 to Friend et al., which is incorporated herein by reference in its entirety. By way of another example, an OLED having a single organic layer may be used. OLEDs may be stacked, such as, for example, as described in U.S. Patent No. 5,707,745 to Forrest et al., which is incorporated herein by reference in its entirety. The OLED structure may deviate from Figure 1 and 2 The simple layer structure described therein. For example, the substrate may include an angled reflective surface to improve out-coupling, such as the mesa structure described in U.S. Patent No. 6,091,195 to Forrest et al., and / or the dimpled structure described in U.S. Patent No. 5,834,893 to Bulovic et al., which are incorporated herein by reference in their entirety.

[0578] Unless otherwise specified, any one of the layers of the various embodiments can be deposited by any suitable method. For organic layers, preferred methods include thermal evaporation, inkjet (as described in U.S. Pat. Nos. 6,013,982 and 6,087,196, which are incorporated by reference in their entirety), organic vapor phase deposition (OVPD) (as described in U.S. Pat. No. 6,337,102 to Forrest et al., which is incorporated by reference in its entirety), and deposition by organic vapor jet printing (OVJP, also known as organic vapor jet deposition (OVJD)) (as described in U.S. Pat. No. 7,431,968, which is incorporated by reference in its entirety). Other suitable deposition methods include spin coating and other solution-based processes. Solution-based processes are preferably carried out in nitrogen or an 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 deposition through a mask, photolithography, and cold welding (as described in U.S. Pat. Nos. 6,294,398 and 6,468,819, which are incorporated by reference in their entirety) and patterning associated with some of the deposition methods such as inkjet and organic vapor jet printing (OVJP). Other methods can also be used. The materials to be deposited can be modified to make them suitable for the specific deposition method. For example, branched or unbranched substituents, preferably containing at least 3 carbons such as alkyl and aryl groups, can be used in small molecules to enhance their ability to withstand solution processing. Substituents having 20 or more carbons can be used, and a range of 3 to 20 carbons is preferred. Materials having an asymmetric structure can have better solution processability than materials having a symmetric structure because asymmetric materials may have a lower tendency to recrystallize. Dendrimer substituents can be used to enhance the ability of small molecules to withstand solution processing.

[0579] Devices fabricated in accordance with embodiments of the present disclosure may further optionally include a barrier layer. One use of the barrier layer is to protect the electrodes and organic layers from damage by harmful substances in an environment exposed to, including moisture, vapor, and / or gases. The barrier layer may be deposited on the substrate, on the electrodes, under the substrate, under the electrodes, beside the substrate, beside the electrodes, or on any other part of the device (including the edges). The barrier layer may include a single layer or multiple layers. The barrier layer may be formed by various known chemical vapor deposition techniques and may include compositions having a single phase and compositions having multiple phases. Any suitable material or combination of materials may be used for the barrier layer. The barrier layer may incorporate inorganic compounds or organic compounds or both. Preferred barrier layers include multiple alternative layers of the following materials: polymeric materials and non-polymeric materials; organic materials and inorganic materials; or mixtures of polymeric materials and non-polymeric 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 entireties.

[0580] Devices fabricated in accordance with embodiments of the present disclosure can be incorporated into a wide variety of electronic component modules (or units), which can in turn be incorporated into a variety of electronic products or intermediate components. Examples of such electronic products or intermediate components include display screens, lighting devices (such as discrete light source devices or lighting panels) that can be utilized by end-user product manufacturers, and the like. The electronic component modules can optionally include driving electronics and / or a power source. Devices fabricated in accordance with embodiments of the present disclosure can be incorporated into a wide variety of consumer products that have one or more electronic component modules (or units) incorporated therein. Disclosed is a consumer product that includes an OLED which includes a compound of the present disclosure in an organic layer of the OLED. The consumer product should include any type of product that includes one or more light sources and / or one or more of a certain type of visual display. Some examples of the consumer product include flat panel displays, curved displays, computer monitors, medical monitors, televisions, billboards, lights for interior or exterior illumination and / or signaling, head-up displays, fully or partially transparent displays, flexible displays, rollable displays, foldable displays, stretchable displays, laser printers, telephones, cellular telephones, tablet computers, phablets, personal digital assistants (PDAs), wearable devices, laptop computers, digital cameras, video cameras, viewfinders, microdisplays (displays having a diagonal of less than 2 inches), 3-D displays, virtual reality or augmented reality displays, vehicles, video walls that include a plurality of displays tiled together, theater or stadium screens, light therapy devices, and signs. A variety of control mechanisms can be used to control devices fabricated in accordance with the present disclosure, including passive matrix and active matrix. Many of the devices are intended to be used in a temperature range that is comfortable for humans, such as from 18 °C to 30 °C, and more preferably at room temperature (20 - 25 °C), but can be used outside of this temperature range (e.g., from -40 °C to +80 °C).

[0581] More 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.

[0582] 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 employ the materials and structures. More generally, organic devices such as organic transistors can employ the materials and structures.

[0583] 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 semi-transparent. In some embodiments, the OLED further includes a layer comprising carbon nanotubes. In some embodiments, the OLED further includes one or more quantum dots. Such quantum dots may be in the emissive layer or in other functional layers, such as a down-conversion layer.

[0584] In some embodiments, the OLED includes an RGB pixel arrangement or a white plus color filter pixel arrangement. 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 less than 10 inches or an area 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.

[0585] Other materials used in D.OLED

[0586] The materials described herein are various examples of specific layers that can be used in an OLED. It can also be used in combination with a wide variety of other materials present in the device. For example, the emissive dopants disclosed herein can be used by the emissive dopants in the EML itself or in combination with a wide variety of other emitters, hosts, transport layers, blocking layers, injection 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 easily consult the literature to identify other materials that can be used in combination.

[0587] a) Conductive dopants:

[0588] The charge transport layer can be doped with a conductive dopant to generally change its charge carrier density, which in turn will change its conductivity. Conductivity is increased by generating charge carriers in the matrix material, and depending on the type of dopant, a change in the Fermi level of the semiconductor can also be achieved. The hole transport layer can be doped with a p-type conductive dopant, and an n-type conductive dopant is used in the electron transport layer. In some embodiments, the conductive dopant includes 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 extended by an acyclic double bond.

[0589] b) HIL / HTL:

[0590] The hole injection / transport materials used in the present disclosure are not particularly limited, and any compound can be used as long as the compound is commonly used as a hole injection / transport material. Examples of the materials include (but are not limited to): phthalocyanine or porphyrin derivatives; aromatic amine derivatives; indolocarbazole derivatives; fluorocarbon-containing polymers; polymers with conductive dopants; conductive polymers such as PEDOT / PSS; self-assembled monomers derived from compounds such as phosphonic acid and silane derivatives; metal oxide derivatives such as MoO x ; p-type semi-conductive organic compounds such as 1,4,5,8,9,12-hexaazatriphenylenehexacarbonitrile; metal complexes; and crosslinkable compounds.

[0591] Examples of aromatic amine derivatives for HIL or HTL include (but are not limited to) the following general structures:

[0592]

[0593] Ar 1 to Ar 9 Each of which is selected from the group consisting of aromatic hydrocarbon cyclic compounds such as: benzene, biphenyl, terphenyl, triphenylene, naphthalene, anthracene, fluorene, phenanthrene, fluorene, pyrene, perylene and azulene; the group consisting of aromatic heterocyclic compounds such as: dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuranopyridine, furanodipyridine, benzothiophenopyridine, thiophenodipyridine, benzoselenophenopyridine and selenophenodipyridine; and the group consisting of 2 to 10 cyclic structural units, which are the same type or different types of groups selected from aromatic hydrocarbon ring groups and aromatic heterocyclic groups and are bonded to each other directly or via at least one of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, a chain structural unit and an aliphatic ring group. Ar 1 to Ar 9 Each of which may be unsubstituted or may be substituted with a general substituent as described above, and any two substituents may be joined or fused into a ring.

[0594] In some embodiments, each Ar 1 to Ar 9 independently comprises a moiety selected from the group consisting of:

[0595]

[0596] where k is an integer from 1 to 20; X 101 to X 108 is C or N; Z 101 is C, N, O or S.

[0597] Examples of metal complexes used in HIL or HTL include, but are not limited to, the following general formula:

[0598] where Met is a metal with an atomic weight greater than 40; (Y 101 -Y 102 ) is a bidentate ligand, and the coordinating atoms of Y 101 and Y 102 are independently selected from C, N, O, P and S; L 101 is another ligand; k' is an integer value from 1 to the maximum number of ligands that can be connected to the metal; and k'+k" is the maximum number of ligands that can be connected to the metal.

[0599] In some embodiments, (Y 101 -Y 102 ) is a 2-phenylpyridine or 2-phenylimidazole derivative. In some embodiments, (Y 101 -Y 102 ) 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 minimum oxidation potential in solution of less than about 0.6 V compared to Fc + / Fc coupling.

[0600] In some embodiments, the HIL / HTL material is selected from the group consisting of: phthalocyanine and porphyrin compounds, starburst triarylamine, CF x fluorohydrocarbon 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 semi-conductive organic complexes, organometallic metal complexes, crosslinkable compounds, polythiophene-based polymers and copolymers, triarylamines, triarylamines containing a spirofluorene core, arylamine carbazole compounds, triarylamines containing (di)benzothiophene / (di)benzofuran, indolocarbazole, isoindole compounds and metal carbene complexes.

[0601] c) EBL:

[0602] An electron blocking layer (EBL) can be used to reduce the number of electrons and / or excitons leaving the emissive layer. The presence of such a blocking layer in a device can result in generally higher efficiency and / or longer lifetime compared to a similar device lacking a blocking layer. Additionally, a blocking layer can be used to confine emission to a desired region of the OLED. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and / or 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 hosts in the EML. In some embodiments, the compound used in the EBL contains the same molecule or the same functional group as one of the hosts described below.

[0603] d) Host:

[0604] The light-emitting layer of the organic EL device of the present disclosure 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.

[0605] Examples of metal complexes used as hosts preferably have the following general formula:

[0606]

[0607] where Met is a metal; (Y 103 -Y 104 ) is a bidentate ligand, and the coordinating atoms of Y 103 and Y 104 are independently selected from C, N, O, P, and S; L 101 is another ligand; k' is an integer value from 1 to the maximum number of ligands that can be connected to the metal; and k'+k" is the maximum number of ligands that can be connected to the metal.

[0608] In some embodiments, the metal complex is:

[0609]

[0610] where (O-N) is a bidentate ligand having a metal coordinated to O and N atoms.

[0611] In some embodiments, Met is selected from Ir and Pt. In another embodiment, (Y 103 -Y 104 ) is a carbene ligand.

[0612] In some embodiments, the host compound contains at least one selected from the following groups: the group consisting of aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, fluoranthene, phenanthrene, fluorene, pyrene, perylene, and azulene; the group consisting of aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, aza-carbazole, aza-indolocarbazole, aza-triphenylene, aza-tetraphenylene, 5λ 2 -benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, 5,9-dioxa-13b-borata-naphtho[3,2,1-de]anthracene; and the group consisting of 2 to 10 cyclic structural units, which are the same type or different types of groups selected from aromatic hydrocarbon ring groups and aromatic heterocyclic groups and are bonded to each other directly or via at least one of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, a chain structural unit, and an aliphatic ring group. Each option within each group may be unsubstituted or may be substituted with a general substituent as described herein or may be further fused.

[0613] In some embodiments, the host compound contains at least one selected from the moieties consisting of the following:

[0614] where k is an integer from 0 to 20 or from 1 to 20. X 101 to X 108 are independently selected from C or N. Z 101 and Z 102 are independently selected from C, N, O, or S.

[0615] In some embodiments, the host material is selected from the group consisting of arylcarbazole, metal 8-hydroxyquinolinate (e.g., alq3, balq), metal phenoxybenzothiazole compounds, conjugated oligomers and polymers (e.g., polyfluorene), aromatic condensed rings, zinc complexes, based on Compounds, aryltriptycene compounds, polycondensed heteroaryl compounds, donor-acceptor type molecules, dibenzofuran / dibenzothiophene compounds, polymers (e.g., pvk), spirofluorene compounds, spirofluorene-carbazole compounds, indolocarbazole, 5-membered ring electron-deficient heterocycles (e.g., triazole, oxadiazole), perylene 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, carbazole linked by non-conjugated groups, azacarbazole / dibenzofuran / dibenzothiophene compounds, and high triplet metal organometallic complexes (e.g., metal-carbene complexes).

[0616] e) Emitter materials in the EML:

[0617] One or more emitter materials can be used in combination with the compounds or devices of the present disclosure. The emitter materials can be emissive or non-emissive in the current devices as described herein. Examples of emitter materials are not particularly limited, and any compound can be used as long as the compound can produce emission in a conventional OLED device. Examples of suitable emitter materials include, but are not limited to, compounds capable of producing 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 a combination of these methods.

[0618] In some embodiments, the emitter material has the formula M(L 1 ) x (L 2 ) y (L 3 ) z ;

[0619] wherein L 1 , L 2 and L 3 can be the same or different;

[0620] wherein x is 1, 2 or 3;

[0621] wherein y is 0, 1 or 2;

[0622] wherein z is 0, 1 or 2;

[0623] wherein x + y + z is the oxidation state of the metal M;

[0624] wherein L 1 is selected from the group consisting of the structures in the following ligand list:

[0625]

[0626]

[0627] where each L 2 and L 3 is independently selected from the group consisting of and the structures in the ligand list; wherein:

[0628] M is selected from the group consisting of: Ir, Rh, Re, Ru, Os, Pt, Pd, Zn, Au, Ag, and Cu;

[0629] T is selected from the group consisting of: B, Al, Ga, and In;

[0630] K 1' is a direct bond or is selected from the group consisting of NR e 、PR e 、O, S, and Se;

[0631] Each Y 1 to Y 15 is independently selected from the group consisting of carbon and nitrogen;

[0632] Y' is selected from the group consisting of 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 ;

[0633] Each R a 、R b 、R c and R d can independently represent mono-substituted to the maximum possible number of substitutions or unsubstituted;

[0634] Each R a1 、R b1 、R c1 、R d1 、R a 、R b 、R c 、R d 、R e and R f is independently hydrogen or a substituent selected from the group of general substituents as defined herein; and

[0635] wherein any two substituents can be fused or joined to form a ring or form a polydentate ligand.

[0636] In some embodiments, the emitter material is selected from the group consisting of the following dopant group 1:

[0637]

[0638]

[0639]

[0640]

[0641] wherein

[0642] X 96 to X 99 each independently is C or N;

[0643] each Y 100 is independently selected from the group consisting of NR”, O, S, and Se;

[0644] R 10a , R 20a , R 30a , R 40a and R 50a each independently represents mono-substituted, up to maximum substitution, or unsubstituted;

[0645] R, R', R”, R 10a , R 11a , R 12a , R 13a , R 20a , R 30a , R 40a , R 50a , R 60 , R 70 , R 97 , R 98 and R 99 each independently is hydrogen or a substituent selected from the group consisting of the general substituents defined herein; any two substituents may be joined or fused to form a ring.

[0646] In some embodiments, the emitter material is selected from the group consisting of the following dopant group 2:

[0647]

[0648]

[0649]

[0650]

[0651]

[0652] Wherein:

[0653] Each Y 100 is independently selected from the group consisting of NR″, O, S, and Se;

[0654] L is independently selected from the group consisting of: a 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;

[0655] X 100 and X 200 are each independently selected from the group consisting of O, S, Se, NR″, and CR″R″′ upon each occurrence;

[0656] Each R A” 、R B” 、R C” 、R D” 、R E” and R F” independently represents mono-substituted, up to maximally substituted, or unsubstituted;

[0657] R, R′, R″, R″′, R A1' 、R A2' 、R A” 、R B” 、R C” 、R D” 、R E” 、R F” 、R G” 、R H” 、R I” 、R J” 、R K” 、R L” 、R M” and R N” each independently is hydrogen or a substituent selected from the group consisting of general substituents as defined herein; any two substituents may be joined or fused to form a ring.

[0658] In some embodiments of the above dopant groups 1 and 2, each unsubstituted aromatic carbon atom may be replaced by N to form a heterocycle. In some embodiments, the maximum number of N atoms in a ring is 1 or 2. In some embodiments of the above dopant group 2, each Pt atom in the formula may be replaced by a Pd atom.

[0659] In some embodiments of the OLED, 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-metal complex. In some embodiments, the delayed fluorescence material is a Zn, Cu, Ag or Au complex.

[0660] In some embodiments of the OLED, the delayed fluorescence material has the formula M(L 5 )(L 6 ), where M is Cu, Ag or Au, and L 5 and L 6 are different, and L 5 and L 6 are independently selected from the group consisting of:

[0661]

[0662]

[0663] where A 1 -A 9 are each independently selected from C or N;

[0664] Each R P , R Q and R U independently represents mono-substituted, up to maximum substitution or unsubstituted;

[0665] where each R P , R P , R U , R SA , R SB , R RA , R RB , R RC , R RD , R RE and R RF are independently hydrogen or a substituent selected from the group of general substituents as defined herein; any two substituents may be joined or fused to form a ring.

[0666] In some embodiments of the OLED, the delayed fluorescence material comprises at least one of the donor moieties selected from the group consisting of:

[0667]

[0668]

[0669] where Y T , Y U , Y V and Y WEach independently selected from the group consisting of: B, C, Si, Ge, N, P, O, S, Se, C═O, S═O and SO2.

[0670] 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 at most three carbon ring atoms together with its substituents can be replaced by N.

[0671] In some embodiments, the delayed fluorescence material comprises at least one selected from the group consisting of acceptor moieties: 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 the donor moiety as described herein can be directly connected, connected via a conjugated linking group or a non-conjugated linking group (such as sp 3 carbon or silicon atom).

[0672] In some embodiments, the fluorescent material comprises at least one selected from the group consisting of chemical moieties:

[0673]

[0674]

[0675] where Y F 、Y G 、Y H and Y I Each independently selected from the group consisting of: B, C, Si, Ge, N, P, O, S, Se, C═O, S═O and SO2;

[0676] where X F and X G Each independently selected from the group consisting of C and N.

[0677] 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 at most three carbon ring atoms together with its substituents can be replaced by N.

[0678] f) HBL:

[0679] A hole blocking layer (HBL) can be used to reduce the number of holes and / or excitons leaving the emissive layer. The presence of such a blocking layer in a device can result in generally higher efficiency and / or longer lifetime compared to a similar device lacking a blocking layer. In addition, a blocking layer can be used to confine emission to a desired region of the OLED. In some embodiments, the HBL material has a lower HOMO (farther from the vacuum level) and / or a higher triplet energy compared to one or more of the emitters closest to the HBL interface.

[0680] In some embodiments, the compound used in the HBL contains the same molecule or the same functional group as used in the host described above.

[0681] In some embodiments, the compound used in the HBL comprises at least one of the following moieties selected from the group consisting of:

[0682] where k is an integer from 1 to 20; L 101 is another ligand, and k' is an integer from 1 to 3.

[0683] g) ETL:

[0684] The electron transport layer (ETL) can include a material capable of transporting electrons. The electron transport layer can 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 can be used as long as it is commonly used to transport electrons.

[0685] In some embodiments, the compound used in the ETL contains at least one of the following moieties in the molecule:

[0686]

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

[0688] In some embodiments, the metal complex used in the ETL contains, but is not limited to, the following general formula:

[0689]

[0690] where (O-N) or (N-N) is a bidentate ligand having a metal coordinated to atoms O, N, or N, N; L 101 is another ligand; k' is an integer value from 1 to the maximum number of ligands that can be attached to the metal.

[0691] In some embodiments, the ETL material is selected from the group consisting of: anthracene - benzimidazole compounds, azatriphenylene derivatives, anthracene - benzothiazole compounds, metal 8 - hydroxyquinolinates, metal hydroxybenzoquinolinates, bathocuprine compounds, 5 - membered ring electron - deficient heterocycles (e.g., triazole, oxadiazole, imidazole, benzimidazole), silole compounds, arylborane compounds, fluorinated aromatic compounds, fullerenes (e.g., C60), triazine complexes, and Zn(N^N) complexes.

[0692] h) Charge - generating layer (CGL)

[0693] In a tandem or stacked OLED, the CGL plays a fundamental role in performance and consists of an n - doped layer and a p - doped layer for injecting electrons and holes, respectively. Electrons and holes are supplied by the CGL and the electrodes. The 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 include n - and p - conductivity dopants used in the transport layer.

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

[0695] It should be understood that the various embodiments described herein are by way of example only and are not intended to limit the scope of the invention. For example, many of the materials and structures described herein can be replaced with other materials and structures without departing from the spirit of the invention. The invention as claimed can thus 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 the various theories as to why the invention works are not intended to be limiting.

[0696] E. Experimental section of the present disclosure

[0697] a) Preparation of exemplary compounds

[0698]

[0699] A 500 mL two-necked round-bottom flask equipped with a rubber septum and a magnetic stir bar was evacuated under vacuum for 10 minutes and then backfilled with nitrogen. Then, 2,6-diisopropylaniline (6.0 g, 6.4 mL, 33.84 mmol, 1 equiv) was transferred into it with 130 mL of anhydrous toluene. This solution was cooled in an ice bath (0 °C), and trimethylaluminum (2.0 M in hexanes, 23.7 mL, 47.38 mmol, 1.4 equiv) was added dropwise. The reaction mixture was allowed to warm to room temperature over 2 hours. Next, a 50 mL anhydrous toluene solution of benzonitrile (4.54 g, 5 mL, 44.00 mmol, 1.3 equiv) was added thereto, and the resulting mixture was stirred under nitrogen at 70 °C overnight. After cooling to room temperature, the reaction mixture was poured into 2:1 (v / v) DCM:MeOH (250 mL) with 50 g of silica gel. This mixture was filtered off, and the silica plug was washed repeatedly with 2:1 (v / v) DCM:MeOH. The filtrate was concentrated under vacuum to give an off-white solid. This solid material was further triturated with heptane (200 mL) to give 6.5 g of N-(2,6-diisopropylphenyl)benzamidine (68% yield), which was used without further purification.

[0700]

[0701] 7-Bromo-5,9-dioxa-13b-boraperylene[3,2,1-de]anthracene (14.0 g, 40.12 mmol, 1 equiv) and N-chlorosuccinimide (NCS, 6.96 g, 52.15 mmol, 1.3 equiv) were added sequentially to a 1000 mL three-necked round-bottom flask equipped with two rubber septa and a magnetic stir bar. Subsequently, a reflux condenser was attached to the flask, and dichloroethane (DCE, anhydrous, 400 mL) was added to the mixture, and the suspension was purged with nitrogen for 15 minutes. Then the flask was transferred to a preheated oil bath at 90 °C, and the mixture was stirred under a positive nitrogen pressure at the same temperature for 40 hours. After cooling to room temperature, the reaction mixture was concentrated under reduced pressure, and then saturated aqueous sodium carbonate (80 mL) was added. Then this suspension was stirred at room temperature for 15 minutes and then transferred to a 1000 mL separatory funnel with DCM (200 mL). Then the aqueous layer was extracted with additional DCM (5 × 100 mL). Then the combined organic matter was further washed with brine, dried over Na2SO4 and concentrated under reduced pressure to give an off-white solid. Toluene (500 mL) was added to this solid, and the suspension was heated at 100 °C (in an oil bath) until all the solid dissolved. The solution was removed from the heating and allowed to cool slowly to room temperature over 16 hours, during which the desired product crystallized out. The colorless crystals were collected by vacuum filtration and the solid was rinsed with more toluene (200 mL) to give 7.5 g of 7-bromo-6-chloro-5,9-dioxa-13b-boraperylene[3,2,1-de]anthracene (49% yield).

[0702]

[0703] N-(2,6-Diisopropylphenyl)benzamidine (2.44 g, 8.69 mmol, 1 equiv), 7-bromo-6-chloro-5,9-dioxa-13b-boraperylene[3,2,1-de]anthracene (4.00 g, 10.43 mmol, 1.2 equiv), cesium carbonate (9.91 g, 30.43 mmol, 3.5 equiv), Xantphos (0.251 g, 0.435 mmol, 5 mol%) and Molecular sieve (0.2 g, 4 - 8 mesh). The pressure vessel containing the solid reagents was evacuated under vacuum for 5 minutes and then backfilled with nitrogen. Xylene (30 mL) was added and the solution was purged with nitrogen for 15 minutes. Tris(dibenzylideneacetone)dipalladium(0) (0.318 g, 4 mol%) was added, and then the reaction vessel was sealed and transferred to a preheated oil bath at 190 °C and stirred for 45 hours. After cooling to room temperature, the mixture was diluted with DCM (20 mL), filtered through a Celite / diatomaceous earth plug and washed with DCM (20 mL). The combined organic extracts were concentrated, the resulting residue was dissolved in the minimum amount of DCM, and then silica gel was added. After drying, the solid material was purified by silica gel column chromatography to give 1.1 g of 13-(2,6 - diisopropylphenyl)-12 - phenyl - 13H - 9,14 - dioxo - 11,13 - diaza - 4b - boratricyclo[4.4.0.02,7]deca - 3,5,7,9 - tetraene in the form of a yellow solid (23% yield).

[0704]

[0705] An iridium complex (288 mg, 1 equiv, 366 μmol), 13-(2,6 - diisopropylphenyl)-12 - phenyl - 13H - 9,14 - dioxo - 11,13 - diaza - 4b - boratricyclo[4.4.0.02,7]deca - 3,5,7,9 - tetraene (0.200 g, 1 equiv, 366 μmol), triethylamine (37.0 mg, 1 equiv, 366 μmol) and 1 - butanone (10.00 mL) were charged into a 50 ml round - bottom flask. The reaction mixture was heated to 66 °C and maintained for 71 hours. The reaction mixture was concentrated to dryness, diluted with 500 mL of dioxane, and photolyzed. The reaction progress was monitored by LC / MS. After the reaction was completed; the reaction mixture was evaporated to dryness and subjected to column chromatography (SiO2, heptane / toluene = 1:1) to give Compound 1 of the present invention. (50 mg; 12% yield)

[0706]

[0707] A 500 mL two-neck round-bottom flask equipped with a rubber septum and a magnetic stir bar was evacuated under vacuum for 10 minutes and then backfilled with nitrogen. Subsequently, 5-(tert-butyl)-[1,1'-biphenyl]-2-amine (10 g, 44.38 mmol, 1 equiv) was transferred therein with 167 mL of anhydrous toluene. This solution was cooled in an ice bath (0 °C), and trimethylaluminum (2.0 M in hexanes, 31.07 mL, 62.13 mmol, 1.4 equiv) was added dropwise. The reaction mixture was allowed to warm to room temperature over 2 hours. Next, an 83 mL anhydrous toluene solution of 3-methoxybenzonitrile (7.68 g, 7.05 mL, 57.69 mmol, 1.3 equiv) was added to the resulting mixture, and the mixture was stirred overnight at 70 °C under nitrogen. After cooling to room temperature, the reaction mixture was poured into 2:1 (v / v) DCM:MeOH (450 mL) with 70 g of silica gel. This mixture was filtered off, and the silica plug was washed repeatedly with 2:1 (v / v) DCM:MeOH. The filtrate was concentrated in vacuo to give an off-white solid. This solid material was further triturated with heptane (400 mL) to give 10.0 g of N-(5-(tert-butyl)-[1,1'-biphenyl]-2-yl)-3-methoxybenzamidine (63% yield), which was used without further purification.

[0708]

[0709] A flame-dried 350 mL pressure vessel equipped with a magnetic stir bar was charged with N-(5-(tert-butyl)-[1,1'-biphenyl]-2-yl)-3-methoxybenzamidine (2.9 g, 8.09 mmol, 1 equiv), 7-bromo-6-chloro-5,9-dioxo-13b-boraperylene[3,2,1-de]anthracene (3.72 g, 9.71 mmol, 1.2 equiv), cesium carbonate (9.23 g, 28.31 mmol, 3.5 equiv), Xantphos (0.234 g, 0.405 mmol, 5 mol%) and Molecular sieve (0.2 g, 4 - 8 mesh). The pressure vessel containing the solid reagent was evacuated under vacuum for 5 minutes and then backfilled with nitrogen. Xylene (30 mL) was added and the solution was purged with nitrogen for 15 minutes. Tris(dibenzylideneacetone)dipalladium(0) (0.297 g, 4 mol%) was added thereto, and then the reaction vessel was sealed and transferred to a preheated oil bath at 190 °C and stirred for 45 hours. After cooling to room temperature, the mixture was diluted with DCM (20 mL), filtered through a diatomaceous earth plug and washed with DCM (20 mL). The combined organic extracts were concentrated, the resulting residue was dissolved in a small amount of DCM, and then silica gel was added. After drying, the solid material was purified by silica gel column chromatography to obtain 13-(5-(tert-butyl)-[1,1'-biphenyl]-2-yl)-12-(3-methoxyphenyl)-13H-9,14-dioxa-11,13-diaza-4b-boratricyclo[4.4.0.02,7]deca-1(6),2,4,6,8-pentaene, 2.3 g (45% yield) as a yellow solid.

[0710]

[0711] Under nitrogen, 13-(5-(tert-butyl)-[1,1'-biphenyl]-2-yl)-12-(3-methoxyphenyl)-13H-9,14-dioxa-11,13-diaza-4b-boratricyclo[4.4.0.02,7]deca-1(6),2,4,6,8-pentaene (2.500 g, 1 equivalent, 4.003 mmol) was dissolved in dichloromethane (40.03 mL). The resulting solution was cooled to 0 °C, and then boron tribromide (2.006 g, 8.006 mL, 1.000 mole, 2 equivalents, 8.006 mmol) was added dropwise. The reaction mixture was stirred at 0 °C for 10 minutes, then warmed to room temperature and stirred for an additional 16 hours. Then the mixture was cooled to 0 °C and quenched with 10 mL of water. Then the mixture was transferred to a separatory funnel and the layers were separated. The organic layer was washed with water (3 × 20 mL), then dried over magnesium sulfate, filtered and evaporated to dryness to obtain 3-(13-(5-(tert-butyl)-[1,1'-biphenyl]-2-yl)-13H-9,14-dioxa-11,13-diaza-4b-boratricyclo[4.4.0.02,7]deca-1(6),2,4,6,8-pentaene-12-yl)phenol (2.550 g, 3.8 mmol, 94%, 90% purity), which was used without further purification.

[0712]

[0713] 3-(13-(5-(tert-Butyl)-[1,1'-biphenyl]-2-yl)-13H-9,14-dioxa-11,13-diaza-4b-boratricyclo[14.2.1.02,7]nonadeca-1(19),2,4,6,8,10,12,14,16,18-decaene-12-yl)phenol (2.545 g, 1 eq., 4.169 mmol) was dissolved in dichloromethane (21.00 mL), and then 1,1,1-trifluoro-N-phenyl-N-((trifluoromethyl)sulfonyl)methanesulfonamide (2.300 g, 1.544 eq., 6.438 mmol), 4-dimethylaminopyridine (51.00 mg, 0.1001 eq., 417.5 μmol), and triethylamine (1.31 g, 1.800 mL, 3.10 eq., 12.9 mmol) were added. The resulting solution was stirred at room temperature for 16 h. Then the reaction mixture was diluted with DCM (5 mL) and washed with NH4Cl solution (2 × 10 mL) and brine (10 mL). The aqueous layer was backwashed with DCM (10 mL), and the combined organics were dried over MgSO4, filtered, concentrated, and purified by silica gel column chromatography to give 2.84 g (91.8%) of 3-(13-(5-(tert-Butyl)-[1,1'-biphenyl]-2-yl)-13H-9,14-dioxa-11,13-diaza-4b-boratricyclo[14.2.1.02,7]nonadeca-1(19),2,4,6,8,10,12,14,16,18-decaene-12-yl)phenyl trifluoromethanesulfonate as a yellow solid.

[0714]

[0715] 3-(13-(5-(tert-butyl)-[1,1'-biphenyl]-2-yl)-13H-9,14-dioxa-11,13-diaza-4b-borol[a]naphtho[3,2,1-de]anthracen-12-yl)phenyl trifluoromethanesulfonate (2.841 g, 1 eq, 3.826 mmol), potassium acetate (1.126 g, 3 eq, 11.48 mmol) and 1,4-dioxane (19.13 mL) were added to a multi-necked round-bottom flask. The resulting mixture was bubbled with N2 for 15 minutes followed by the addition of PdCl2(dppf)-DCM adduct (156.2 mg, 0.05 eq, 191.3 μmol). The reaction mixture was stirred at 85°C for 16 hours. The reaction mixture was cooled to room temperature and then filtered through a pad of celite, washing with EtOAc. The volatiles were removed under reduced pressure and the resulting crude residue was then redissolved in DCM, adsorbed onto silica and purified by silica gel column chromatography to afford 0.890 g (32.3%) of 13-(5-(tert-butyl)-[1,1′-biphenyl]-2-yl)-12-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-13H-9,14-dioxa-11,13-diaza-4b-borola[a]naphtho[3,2,1-de]anthracene as a yellow solid.

[0716]

[0717] (3,5-di-tert-butyl-2-methoxyphenyl)boric acid (8.055g, 1.2 equivalents), 4-(tert-butyl)-2-chloropyridine (4.31g, 1 equivalent) and potassium carbonate (10.5g, 3 equivalents) were measured into a round-bottom flask, and 100mL of dioxane and 33mL of water were then added. The mixture was degassed for 15 minutes using nitrogen. Tetrakis(triphenylphosphine)palladium (880mg, 3mol%) was added to the mixture. The flask was equipped with a diaphragm and then transferred to a preheated 100°C oil bath and maintained for 16 hours. The reaction mixture was cooled to room temperature, ethyl acetate (25mL) was added to the mixture and transferred to a separatory funnel. The layers were separated and the water layer was washed four more times with ethyl acetate. The organic layers were combined, washed with brine, dried over sodium sulfate, filtered, concentrated, and purified by silica gel column chromatography to afford 7.94 g (88.0%) of 4-(tert-butyl)-2-(3,5-di-tert-butyl-2-methoxyphenyl)pyridine.

[0718]

[0719] 4-(tert-Butyl)-2-(3,5-di-tert-butyl-2-methoxyphenyl)pyridine (4.55 g, 1 equivalent) was measured into a 500 mL round-bottom flask, and then 170 mL of DCM was added. The mixture was kept under a nitrogen atmosphere. Separately, 3-chloroperbenzoic acid (m-CPBA, 3.331 g, 1.5 equivalents, corresponding to 4.33 g (77% reagent) dissolved in 30 mL of DCM) was slowly added to the main flask via syringe at 0 °C. An additional 20 mL of DCM was used for washing. The mixture was stirred at this temperature for 1 hour, then slowly warmed to room temperature and stirred overnight. The reaction was cooled to 0 °C and 20 mL of saturated aqueous NaHCO3 was slowly added dropwise to the mixture. After the addition was complete, 20 mL of 10% aqueous Na2S2O3 was introduced to quench any remaining amount of peroxide that might be present in the mixture. Finally, an additional 20 mL of 1 M aqueous NaOH was added. The mixture was then transferred to a 2 L separatory funnel and combined with 6 other batches prepared under similar scale conditions (3.34 g, 3.34 g, 3.73 g, 5.03 g, 5.31 g, and 6.50 g of 4-(tert-butyl)-2-(3,5-di-tert-butyl-2-methoxyphenyl)pyridine). The aqueous and organic layers were separated, and the aqueous layer was washed 4 times with 100 mL of DCM. The organic layers were combined and washed twice with 300 mL of 1 M aqueous NaOH (to remove any amount of m-chlorobenzoic acid). Finally, the organic layers were combined, dried over Na2SO4, filtered, concentrated, and purified by silica gel column chromatography to afford 29.17 g (94.7% combined) of 4-(tert-butyl)-2-(3,5-di-tert-butyl-2-methoxyphenyl)pyridine 1-oxide.

[0720]

[0721] 4-(tert-Butyl)-2-(3,5-di-tert-butyl-2-methoxyphenyl)pyridine 1-oxide (9.82 g, 1 equivalent) was added to a two-necked flask, and then DCM (67 mL) and triethylamine (13 mL, 3.5 equivalents) were added. The reactants were kept under a nitrogen atmosphere, and a gas scrubber containing 2 M aqueous NaOH was fitted to the flask. The mixture was stirred at room temperature for 10 minutes, and then phosphoryl chloride (8.6 mL, 3.5 equivalents) was slowly added dropwise to the mixture via syringe. The reactants were stirred at 25 °C overnight. The reaction was quenched by adding approximately 60 mL of water (caution: the reaction of POCl3 with water is delayed, so the addition needs to be carried out very slowly). Once the unreacted POCl3 was quenched with water, 1 M aqueous NaOH was slowly introduced to set the pH of the mixture to basic. The mixture was transferred to a separatory funnel and the layers were separated. The aqueous layer was washed three times with 50 mL of DCM. The organic layers were combined, dried over Na2SO4, filtered and concentrated on a rotary evaporator. The crude material was combined with two other crude batches prepared from 19.35 g and 0.550 g of 4-(tert-butyl)-2-(3,5-di-tert-butyl-2-methoxyphenyl)pyridine 1-oxide, and purified by silica gel column chromatography to give 13.7 g (44.0% combined) of 4-(tert-butyl)-2-chloro-6-(3,5-di-tert-butyl-2-methoxyphenyl)pyridine.

[0722]

[0723] A solution of 4-(tert-butyl)-2-chloro-6-(3,5-di-tert-butyl-2-methoxyphenyl)pyridine (3.99 g, 10.28 mmol) in DCM (165 mL) was cooled to 0 °C and placed under a nitrogen atmosphere with a nitrogen / vacuum cycle (3 times). A solution of 1 M boron tribromide in DCM (15.5 mL, 1.5 equivalents, 15.43 mmol) was added dropwise over 5 minutes, and then the reaction mixture was stirred overnight and allowed to warm to room temperature. The reaction mixture was quenched by adding water (108 mL), and aqueous NaHCO3 (75 mL) was added to adjust the pH to pH 7. The subsequent layers were separated and the aqueous layer was washed with DCM (75 mL). The DCM layers were combined and washed with brine (125 mL). The organic layer was dried over MgSO4, filtered, evaporated to give a brown crude material. The crude material was triturated in cold MeCN (15 mL), and the solid was collected by filtration to give a white solid (2.69 g). The mother liquor was concentrated in vacuo, and the residue was triturated in cold MeCN and the solid was collected by filtration to give a white solid (497 mg). The solids were combined to give 2,4-di-tert-butyl-6-(4-(tert-butyl)-6-chloropyridin-2-yl)phenol as a white solid (3.04 g, 76%).

[0724]

[0725] 2,4-Di-tert-butyl-6-(4-(tert-butyl)-6-chloropyridin-2-yl)phenol (295.0 mg, 1.132 eq, 788.8 μmol), 2,4-Di-tert-butyl-6-(4-(tert-butyl)-6-chloropyridin-2-yl)phenol (295.0 mg, 1.132 eq, 788.8 μmol), tripotassium phosphate (445.0 mg, 3.009 eq, 2.096 mmol) and XPhos Palladacycle (42.00 mg, 0.07661 eq, 53.38 μmol) were added to a reaction vial. The reaction mixture was bubbled with N2 for 15 minutes, and 1,4-dioxane (5.000 mL) and water (500.0 μL) were added. The reaction mixture was heated at 45 °C in a sand bath with stirring for 16 hours. The reaction mixture was filtered through celite, washed with EtOAc, then the volatiles were removed under reduced pressure, and the crude was purified by silica gel column chromatography to give 0.384 g (59.1%) of 2,4-Di-tert-butyl-6-(4-(tert-butyl)-6-(3-(13-(5-(tert-butyl)-[1,1'-biphenyl]-2-yl)-13H-9,14-dioxo-11,13-diaza-4b-boratricyclo[14.4.0.02,11]icos-12-yl)phenyl)pyridin-2-yl)phenol as a yellow solid.

[0726]

[0727] 2,4-Di-tert-butyl-6-(4-(tert-butyl)-6-(3-(13-(5-(tert-butyl)-[1,1'-biphenyl]-2-yl)-13H-9,14-dioxo-11,13-diaza-4b-boratricyclo[14.4.0.02,11]icos-12-yl)phenyl)pyridin-2-yl)phenol (50.00 mg, 1 eq, 53.65 μmol), platinum(II) acetylacetonate (21.10 mg, 1 eq, 53.65 μmol) and 1,2-dichlorobenzene (1.000 mL) were added to a 2 mL microwave vial. The solution was bubbled with N2 for 15 minutes, then the reaction vial was sealed and the mixture was heated to 220 °C under microwave irradiation and maintained for 16 hours. The vial was opened and the reaction volatiles were removed, then the crude mixture was purified by silica gel column chromatography to give 24 mg (40%) of Compound 2 of the present invention as a yellow solid.

[0728]

[0729] A solution of 2-bromo-1,4-dimethoxybenzene (3.00 g, 13.8 mmol, 1.0 equiv), (3-chloro-2-fluorophenyl)boronic acid (2.41 g, 13.8 mmol, 1.0 equiv) and potassium carbonate (3.82 g, 27.6 mmol, 2.0 equiv) in toluene (81 mL) and water (16 mL) was bubbled with nitrogen for 5 minutes. After addition of tetrakis(triphenylphosphine)palladium(0) (0.798 g, 0.691 mmol, 0.05 equiv) under continuous sparging, it was maintained for an additional 5 minutes and heated at 80 °C overnight. Several pre-reactions were combined with this batch. The combined reaction mixture was diluted with water (50 mL) and the layers were separated. The aqueous layer was extracted with dichloromethane (2 × 50 mL), and the combined organic layers were washed with saturated brine (50 mL), dried over sodium sulfate (20 g), filtered and concentrated under reduced pressure. The residue was purified on silica gel using a hexane solution of dichloromethane to give 3-chloro-2-fluoro-2',5'-dimethoxy-1,1'-biphenyl as an oil (2.7 g, 28% yield).

[0730]

[0731] At -78 °C, a solution of 1 M boron tribromide in dichloromethane (38.4 mL, 38.4 mmol, 2.0 equiv) was slowly added to a solution of 3-chloro-2-fluoro-2',5'-dimethoxy-1,1'-biphenyl (4.65 g, 17.4 mmol, 1.0 equiv) in anhydrous dichloromethane (87 mL), and it was warmed to room temperature overnight. The reaction mixture was cooled to 0 °C and quenched slowly with methanol. The reaction mixture was diluted with water (100 mL) and the layers were separated. The aqueous layer was extracted with dichloromethane (2 × 100 mL). The combined organic layers were washed with brine (50 mL), dried over sodium sulfate (20 g), filtered and concentrated under reduced pressure. The residue was purified on silica gel using a hexane solution of dichloromethane to give 3'-chloro-2'-fluoro-[1,1'-biphenyl]-2,5-diol as an oil (2.8 g, 67% yield).

[0732]

[0733] A suspension of 60% sodium hydride (2.6 g, 65.3 mmol, 3.0 equiv) was slowly added to a solution of 3'-chloro-2'-fluoro-[1,1'-biphenyl]-2,5-diol (5.2 g, 21.8 mmol, 1.0 equiv) in N-methylpyrrolidone (50 mL), and the mixture was bubbled with nitrogen for 5 minutes. After heating overnight at 80 °C, the reaction mixture was cooled to 0 °C and carefully basified with sodium bicarbonate solution. The reaction mixture was diluted with dichloromethane (10 mL) and water (10 mL), and the layers were separated. The aqueous layer was extracted with dichloromethane (2 × 100 mL), and the combined organic layers were washed with saturated brine (50 mL), dried over sodium sulfate (25 g), filtered, and concentrated under reduced pressure. The residue was purified on silica gel using a hexane solution of dichloromethane to give 6-chlorodibenzo[b,d]furan-2-ol (2.5 g, 52% yield) as an oil.

[0734]

[0735] Potassium carbonate (15.2 g, 109.6 mmol, 1.1 equiv) was added to a solution of phenol (9.38 g, 99.7 mmol, 1.0 equiv) in N-methylpyrrolidone (60.00 mL), and the mixture was bubbled with nitrogen for 5 minutes. 2-Bromo-1,3-difluorobenzene (25.00 g, 129.5 mmol, 1.3 equiv) was added, and then the mixture was heated at 160 °C for 16 hours. The reaction mixture was cooled to room temperature and diluted with dichloromethane (20 mL) and water (20 mL). The layers were separated, and the aqueous layer was extracted with dichloromethane (2 × 20 mL). The combined organic layers were dried over sodium sulfate (5 g), filtered, and concentrated to approximately 50 mL. This material was purified on silica gel using a hexane solution of dichloromethane to give 2-bromo-1-fluoro-3-phenoxybenzene (16.1 g, 60% yield) as a white solid.

[0736]

[0737] A mixture of 6-chlorodibenzo[b,d]furan-2-ol (1.3 g, 5.95 mmol, 1.0 equiv), 2-bromo-1-fluoro-3-phenoxybenzene (3.97, 14.9 mmol, 2.5 equiv), and cesium carbonate (2.32 g, 7.14 mmol, 1.2 equiv) in N-methylpyrrolidone (30 mL) was bubbled with nitrogen for 5 minutes and then heated at 130 °C overnight. The reaction mixture was cooled to room temperature and purified on silica gel using a hexane solution of dichloromethane to give 2-(2-bromo-3-phenoxyphenoxy)-6-chlorodibenzo[b,d]furan (1.5 g, 54% yield) as a white solid.

[0738]

[0739] A solution of 2-(2-bromo-3-phenoxyphenoxy)-6-chlorodibenz[b,d]furan (3.0 g, 6.42 mmol, 1.0 equiv) in anhydrous toluene (30 mL) was bubbled with nitrogen for 10 minutes and then cooled to -78 °C. A 2.5 M solution of n-butyllithium in hexanes (3.8 mL, 9.66 mmol, 1.55 equiv) was added, and the reaction mixture was warmed to room temperature. After 1 hour, the mixture was cooled to 0 °C and boron tribromide (1.24 mL, 12.9 mmol, 2.0 equiv) was added. After stirring for 3 hours at room temperature, Hunig's base (3.4 mL, 19.3 mmol, 3.0 equiv) was added and the mixture was heated at 130 °C for 24 hours. The reaction mixture was cooled to room temperature and diluted with water (50 mL). The layers were separated, and the aqueous layer was extracted with dichloromethane (2 × 20 mL). The combined organic layers were dried over sodium sulfate (20 g), filtered, and concentrated to approximately 100 mL. This material was purified on silica gel using a hexane solution of dichloromethane to give 14-chloro-5,9,15-trioxa-16b-boraindolo[1,2-b]naphtho[1,2,3-fg]anthracene as a yellow solid (1.0 g, 39% yield).

[0740]

[0741] A 2.5 M solution of n-butyllithium in hexanes (0.54 mL, 2.5 mmol, 2.7 equiv) was added to a solution of 2-bromo-4,5-bis(methyl-d3)pyridine in THF (5 mL) at -78 °C and stirred for 3 hours. A 1.9 M solution of zinc chloride in 2-methyl THF (0.72 mL, 1.4 mmol, 2.7 equiv) was added to the solution, stirred for 1 hour, and then warmed to room temperature. 14-Chloro-5,9,15-trioxa-16b-boraindolo[1,2-b]naphtho[1,2,3-fg]anthracene (0.2 g, 0.5 mmol, 1.0 equiv) and XPhosPalladacycle-G2 (39.8 mg, 0.051 mmol, 0.1 equiv) were added to the solution and heated at 65 °C overnight. The reaction mixture was concentrated, and the residue was purified on silica gel using a hexane solution of dichloromethane to give 2-(5,9,15-trioxa-16b-boraindolo[1,2-b]naphtho[1,2,3-fg]anthracen-14-yl)-4,5-bis(methyl-d3)pyridine as a yellow solid (0.15 g, 62% yield), ligand 3.

[0742]

[0743] An 8 mL vial equipped with a stir bar was charged with ligand 3 (50.00 mg, 1 equiv, 106.1 μmol), dimer 1 (137.2 mg, 1.5 equiv, 159.1 μmol), and acetone (3.536 mL). The mixture was bubbled with nitrogen for 10 minutes and then triethylamine (53.67 mg, 73.9 μL, 5.0 equiv, 530.4 μmol) was added. The system was heated at 60 °C in a sealed vial for 3 hours. The crude mixture was concentrated to dryness and then triturated in methanol to afford a yellow solid. The compound was photoisomerized and then triturated again in methanol to afford the inventive compound 3 as a yellow solid.

[0744] Table 1. DFT Calculations

[0745]

[0746]

[0747]

[0748]

[0749] Calculate the optoelectronic properties of the inventive compounds listed in Table 1. The calculations were performed using the B3LYP functional with the 6-31G* basis set. Geometry optimizations were carried out in vacuo. The excitation energies at these optimized geometries were obtained using time-dependent density functional theory (TDDFT). A continuum solvent model was applied in the TDDFT calculations to mimic the tetrahydrofuran solvent. All calculations were carried out using the program Gaussian.

[0750] The computational results obtained using the DFT function sets and basis sets identified above are theoretical. Comprehensive computational schemes, such as Gaussian using the 6-31G* basis set employed herein (or the CEP-31G basis set that can be used for organometallic molecules), rely on the assumption that electronic effects are additive and thus, can extrapolate to the complete basis set (CBS) limit using larger basis sets. However, when the research goal is to understand the variations in HOMO, LUMO, S1, T1, bond dissociation energies, etc. of a series of structurally related compounds, the additive effects are expected to be similar. Thus, although the absolute error using B3LYP may be significant compared to other computational methods, the relative differences between the HOMO, LUMO, S1, T1, and bond dissociation energy values calculated using the B3LYP protocol are expected to reproduce the experiment reasonably well. See, e.g., Hong et al., Chem. Mater. 2016, 28, 5791-98, 5792-93 and Supplementary Information (discussing the reliability of DFT computational results in the case of OLED materials). Additionally, regarding iridium or platinum complexes applicable in the OLED field, the data obtained from DFT calculations are closely related to actual experimental data. See Tavasli et al., J. Mater. Chem. 2012, 22, 6419-29, 6422 (Table 3) (showing DFT calculations closely related to actual data for various emissive complexes); Morello, G.R., J. Mol. Model. 2017, 23:174 (studying various DFT function sets and basis sets and inferring that the combination of B3LYP and CEP-31G is particularly accurate for emissive complexes).

[0751] The emission spectra of each of Compounds 1-3 of the present invention were measured. As shown in Table 2, RT (room temperature) emission peaks of 499, 539, and 516 nm were obtained from the peak maxima of each phosphorescence emission of degassed solution samples in 2-MeTHF at room temperature. Emission was measured on a Horiba Fluorolog-3 spectrofluorometer equipped with a Synapse Plus CCD detector. All samples were excited at 340 nm. Compounds 1 to 3 of the present invention represent three main core structures of current green / yellow emitters. These experimental results will provide a baseline to correlate with the DFT computational results within each family having a similar core structure. Thus, the compounds of the present invention are considered useful for OLED-related applications, particularly as green emitters.

[0752] Table 2

[0753]

Claims

1. A compound having formula I The structure of the first ligand L A ,in: At least one of the moiety B or the moiety C has a formula II fused thereto structure; Each of moiety A and moiety B is independently a 5- to 10-membered carbocyclic or heterocyclic ring; each of moiety D, moiety E, and, if present, moiety C, is independently a monocyclic or polycyclic fused ring system, wherein each ring of the monocyclic or polycyclic fused ring system is independently a 5- to 10-membered carbocyclic or heterocyclic ring; If moiety A is a 6-membered ring and moiety B is a 5-membered ring, then moiety C is present; Z 1 To Z 6 Each of is independently C or N; L 1 Selected from the group consisting of: direct 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'; Y is selected from the group consisting of 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'; K 1 and K 2 Each of which is independently selected from the group consisting of: direct key, O, S, N (R α )、P(R α )、B(R α )、C(R α )(R β ) and Si(R α )(R β ); R A , R B , R C , R D and R E Each of the above independently represents mono-substitution to the maximum permissible substitution or no substitution; Each R, R', R * , R α , R β , R A , R B , R C , R D and R E are independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, germanyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, seleno, and combinations thereof; L A Coordinate with metal M; The metal M has an atomic mass of at least 40 and can be coordinated with other ligands; L A can be joined with other ligands to form tridentate, tetradentate, pentadentate or hexadentate ligands; and Any two substituents may be joined or fused to form a ring, provided that the compound is not:

2. The compound of claim 1 , wherein each of moiety A and moiety B is independently selected from the group consisting of: benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole and triazole; and / or wherein each of moiety D, moiety E and (if present) moiety C is independently selected from the group consisting of: 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, benzoselenophene, aza-benzoselenophene, indene, aza-indene, indole, aza-indole, benzimidazole, aza-benzimidazole, benzimidazole, aza-benzimidazole, carbazole, aza-carbazole, dibenzofuran, aza-dibenzofuran, dibenzothiophene, aza-dibenzothiophene, quinoxaline, phthalazine, phenanthrene, aza-phenanthrene, anthracene, aza-anthracene, phenanthridine, fluorene and aza-fluorene.

3. The compound according to claim 1, wherein Z 1 C and Z 4 is N or carbene carbon, or wherein Z 1 is N or carbene carbon and Z 4 is C; and / or wherein L 1 is a direct key; and / or wherein K 1 is a direct bond, O or S; and / or wherein K 2 is a direct bond, O or S; and / or wherein Z 2 , Z 3 , Z 5 and Z 6 Each of 2 , Z 3 , Z 5 and Z 6 is N; and / or wherein Y is selected from the group consisting of: O, S, NR, C=O, CRR', SiRR' and Se; and / or wherein R * With R E joined or fused to form Ring E1; and / or Wherein the structure of formula II is fused to part B or part C.

4. The compound according to claim 1, wherein at least one R A comprising a substituent selected from the group consisting of an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, and combinations thereof; and / or wherein at least one R B comprising a substituent selected from the group consisting of an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, and combinations thereof; and / or wherein at least one R C comprising a substituent selected from the group consisting of an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, and combinations thereof; and / or wherein at least one R D comprising a substituent selected from the group consisting of an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, and combinations thereof; and / or wherein at least one R E comprising a substituent selected from the group consisting of: alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof; and / or wherein R * comprising a substituent selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof; and / or wherein the metal M is selected from the group consisting of Ir, Rh, Re, Ru, Os, Pt, Pd, Ag, Au, and Cu.

5. The compound according to claim 1, wherein the ligand L A Select from the group consisting of: in: For each occurrence, each X, Z A1 , Z A2 , Z A3 and Z A4 are independently C or N; k is a linking group selected from the following: 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', and n is An integer selected from 0 to 2; Y A1 , Y A2 , Y A3 and Y A4 each of which is independently selected from the group consisting of: absence of a 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'; Y A1 , Y A2 , Y A3 or Y A4 At least one of the exists; When present, Y A4 Bond to another ligand; R AB , R AC and R AD Each of the above independently represents a single substitution to the maximum permissible substitution, or no substitution; Each R, R', R AB , R AC and R AD are independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, germanyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thiol, sulfinyl, sulfonyl, phosphino, seleno, and combinations thereof; and Any two substituents may be joined or fused to form a ring.

6. The compound according to claim 1, wherein the ligand L A Select from the group consisting of: R AB , R AC , R AD , R AE and R AF Each of the above independently represents a single substitution to the maximum permissible substitution, or no substitution; Each R AB , R AC , R AD , R AE and R AF are independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, germanyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thiol, sulfinyl, sulfonyl, phosphino, seleno, and combinations thereof; and Any two substituents may be joined or fused to form a ring.

7. The compound according to claim 1, wherein the ligand L A Selected from L A i-(Ri)(Rj)(Rk)(Rl), wherein i is an integer from 1 to 79; and each of Ri, Rj, Rk and Rl is independently selected from the group consisting of R1 to R468, and L A 1-(R1)(R1)(R1)(R1) to L A Each of 79-(R468)(R468)(R468)(R468) is defined as follows: Where R1 to R468 have the following structure:

8. The compound according to claim 1, wherein the compound has the formula M(L A ) p (L B ) q (L C ) r , where L B and L C each is a bidentate ligand; and wherein 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 the metal M.

9. The compound according to claim 8, wherein the compound has a formula selected from the group consisting of: 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 ); and where L A , L B and L C Different from each other; or formula Pt(L A )(L B ); and where L A and L B Can be the same or different.

10. The compound according to claim 8, wherein L B and L C Each independently selected from the group consisting of: in: T is selected from the group consisting of B, Al, Ga and In; K 1 'Selected from the group consisting of: single bond, O, S, NR e , PR e , BR e , CR e R f and SiR e R f ; Y 1 To Y 13 Each of is independently selected from the group consisting of C and N; Y'Select from the group consisting of: BR e , BR e R f NR e , PR e 、P(O)R e ,O,S,Se,C=O,C=S,C=Se,C=NR e 、C=CR e R f 、S=O、SO2、CR e R f 、SiR e R f and GeR e R f ; R e and R f may be fused or joined to form a ring; Each R a , R b , R c and R d independently represent mono-substitution to the maximum allowed number of substitutions, or no substitution; R a1 , R b1 , R c1 , R d1 , R a , R b , R c , R d , R e and R f each of which is independently hydrogen or a substituent selected from the group consisting of deuterium, halo, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, germanyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thiol, seleno, sulfinyl, sulfonyl, phosphino, and combinations thereof; and R a1 , R b1 , R c1 , R d1 , R a , R b , R c and R d Any two adjacent substituents of may be fused or joined to form a ring or to form a multidentate ligand.

11. The compound according to claim 8, wherein the compound has the formula Ir(L A )3, Formula Ir(L A )(L Bk )2, Formula Ir(L A )2(L Bk ), formula Ir(L A )2(L Cj-I ) or Ir(L A )2(L Cj-II ), Where L A According to formula I; Where k is an integer from 1 to 836, and each L Bk Has the structure defined as follows: Each L Cj-I Based on the formula structure; and Each L Cj-II Based on the formula The structure of Cj-I and L Cj-II Each L Cj , R 201 and R 202 Defined in the following list: Where R D1 To R D246 With the following structure defined in Listing 9:

12. The compound of claim 1, wherein the compound is selected from the group consisting of:

13. The compound according to claim 8, wherein the compound has formula III: in: M 1 is Pd or Pt; Moieties E' and F' are each independently a monocyclic or polycyclic structure comprising a 5- to 10-membered carbocyclic or heterocyclic ring; Z 3* and Z 4* Each independently is C or N; K 1 , K 2 , K 3 and K 4 are each independently selected from the group consisting of a direct bond, O and S, wherein at least two of them are direct bonds; L 1 , L 2 and L 3 Each independently does not exist or is selected from the group consisting of: direct key, 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', GeRR', alkylene, cycloalkyl, aryl, cycloalkylene, arylene, heteroarylene, and combinations thereof, wherein L 1 and L 2 At least one of the exists; R E ' and R F ' each independently represents zero, a single or up to the maximum allowed number of substitutions on the relevant ring; R, R', R E ' and R F ' each of which is independently hydrogen or a substituent selected from the group consisting of deuterium, halide, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, seleno, sulfinyl, sulfonyl, phosphino, and combinations thereof; and When chemically feasible, two adjacent R A , R B , R C , R E , R E ' and R F ' may be joined or fused together to form a ring.

14. An organic light-emitting device, comprising: anode; cathode; and An organic layer is disposed between the anode and the cathode, wherein the organic layer comprises the compound of claim 1.

15. A consumer product comprising an organic light-emitting device, the organic light-emitting device comprising: anode; cathode; and An organic layer is disposed between the anode and the cathode, wherein the organic layer comprises the compound of claim 1.

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