Organic electroluminescent materials and devices

Abstract

The invention relates to organic electroluminescent materials and devices. A compound having a first ligand LA comprising the structure of Formula I: # imgabs0 # wherein the structure of Formula II # imgabs1 # is fused to at least one of moiety A or moiety B by two or more neighbors of X1 to X11. In Formula I and Formula II, each of Part A and Part B is a monocyclic or polycyclic fused ring system; each of Z1 to Z4 and X1 to X11 is C or N; each of L, YA and YB is a direct bond or a linking group; each of K1 and K2 is a direct bond or a linking group; each RA, RB, RC1, RC2 and RC3 is hydrogen or a universal substituent as defined herein; and LA is coordinated with a metal M having an atomic mass of at least 40. 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 Art

[0004] For various reasons, optoelectronic devices utilizing 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 a cost advantage 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 Invention

[0007] 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:

[0008] In Formula I:

[0009] Each of moiety A and moiety B is independently a monocyclic or polycyclic fused ring system, wherein each ring in the monocyclic or polycyclic fused ring system is independently a 5 - to 10 - membered carbocyclic or heterocyclic ring;

[0010] The structure of Formula II: is fused to at least one of moiety A or moiety B through two or more adjacent ones of X 1 to X 11 ;

[0011] Each of Z 1 to Z 4 and X 1 to X 11 is independently C or N;

[0012] Each of L, Y A and Y B is independently 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] Each of K 1 and K 2 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 );

[0014] Each of R A , R B , R C1 , R C2 and R C3 independently represents mono - substitution to the maximum allowable substitution, or no substitution;

[0015] Each R, R', R α , R β , R A , R B , R C1 、RC2 and R C3 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, selenyl, and combinations thereof;

[0016] L A is coordinated to a metal M having an atomic mass of at least 40;

[0017] The metal M may be coordinated with other ligands; and

[0018] L A may be joined with other ligands to form a tridentate, tetradentate, pentadentate, or hexadentate ligand.

[0019] In another aspect, the present disclosure provides a formulation comprising a compound having a first ligand L A wherein the first ligand L A comprises the structure of Formula I as described herein.

[0020] In yet 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 L A comprises the structure of Formula I as described herein.

[0021] In yet 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 L A comprises the structure of Formula I as described herein. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 Discloses an organic light emitting device.

[0023] Figure 2 Discloses an inverted organic light emitting device without an independent electron transport layer. DETAILED DESCRIPTION

[0024] A. Terms

[0025] Unless otherwise specified, the following terms used herein are defined as follows:

[0026] As used herein, "top" means furthest from the substrate, and "bottom" means closest to the substrate. In cases where a first layer is described as being "disposed on" a second layer "above", the first layer is disposed further from the substrate. Unless the first layer is specified as "in contact with" the second layer, other layers may be present between the first and second layers. For example, the cathode may be described as being "disposed on" the anode "above" even though various organic layers are present between the cathode and the anode.

[0027] As used herein, "solution processable" means capable of being dissolved, dispersed, or transported in a liquid medium in the form of a solution or suspension and / or deposited from a liquid medium.

[0028] 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.

[0029] 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 generally 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 further from the vacuum level in the downward direction. Thus, the definitions of HOMO and LUMO energy levels follow different rules than the work function.

[0030] 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 on top of each other in a stacked manner.

[0031] As used herein, a "NIR," "red," "green," "blue," or "yellow" layer, material, region, or device refers to a layer, material, region, or device that emits light in a wavelength range of about 700-1500 nm, 580-700 nm, 500-600 nm, 400-500 nm, or 540-600 nm, respectively, or a layer, material, region, or device having the highest emission spectrum peak in the corresponding wavelength region. In some arrangements, separate regions, layers, materials, or devices may provide separate "deep blue" and "light blue" emissions. As used herein, a "deep blue" emission component refers to an emission 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 "deep blue" emission component is in the range of about 400-470 nm, but these ranges may vary for some configurations.

[0032] In some arrangements, a color-changing layer is provided that converts, modifies or changes the color of light emitted by another layer to an emission having a different wavelength. This color-changing layer can be configured to shift the wavelength of 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. In general, there are two types of color-changing layers: color filters that modify the spectrum by removing light of non-desired wavelengths, and color-changing layers that convert higher energy photons into lower energy. For example, there may be a "red" filter to filter the input light to remove light with wavelengths outside the range of about 580-700nm. A component of "color" refers to a component that produces or otherwise emits light having a specific color as previously described when activated or used. For example, a "first emission region of a first color" and a "second emission region of a second color different from the first color" describe two emission regions that emit two different colors as previously described when activated within the device.

[0033] As used herein, emissive materials, layers, and regions may be distinguished from each other and from other structures based on the light that the material, layer, or region initially produces as opposed to the light that the same or different structure ultimately emits. Initial light generation is typically the result of a change in energy levels that results in photon emission. For example, an organic emissive material may initially produce blue light, which may be converted to red or green light by a color filter, quantum dots, or other structure, such that the complete emissive stack or sub-pixel emits red or green light. In this case, the initial emissive material, region, or layer may be referred to as the "blue" component, even if the sub-pixel is the "red" or "green" component.

[0034] In some cases, it may be preferable to describe the color of a component, such as the color of an emission region, a sub-pixel, a color-changing layer, etc., according to 1931 CIE coordinates. For example, a yellow-emitting material may have multiple peak emission wavelengths, one in or near the edge of the "green" region and one in or near the edge of the "red" region, as previously described. 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:

[0035]

[0036] The terms "halo", "halogen", and "halo group" may be used interchangeably and refer to fluorine, chlorine, bromine, and iodine.

[0037] The term "acyl" refers to a substituted carbonyl (-C(O)-R s ).

[0038] The term "ester" refers to a substituted oxycarbonyl (-O-C(O)-R s or -C(O)-O-R s ) group.

[0039] The term "ether" refers to an -OR s group.

[0040] The terms "sulfanyl" or "thioether" may be used interchangeably and refer to an -SR s group.

[0041] The term "selenoalkyl" refers to a -SeR s group.

[0042] The term "sulfinyl" refers to a -S(O)-R s group.

[0043] The term "sulfonyl" refers to a -SO2-R s group.

[0044] The term "phosphino" 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.

[0045] The term "silyl" 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 groups, where each R s can be the same or different.

[0046] The term "germyl" refers to a group containing at least one germanium atom bonded to the relevant structure. Common examples of germyl include, but are not limited to, groups such as -Ge(R s )3 groups, where each R s can be the same or different.

[0047] The term "boryl" refers to a group containing at least one boron atom bonded to the relevant structure. Common examples of boryl include, but are not limited to, groups such as -B(R s )2 groups or their Lewis adducts -B(R s )3 groups, where R s can be the same or different.

[0048] In each of the above, R s can 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.

[0049] 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 can be further substituted.

[0050] 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 can be further substituted.

[0051] 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.

[0052] 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 from two to fifteen carbon atoms. Additionally, the alkenyl, cycloalkenyl, or heteroalkenyl may be further substituted.

[0053] 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 from two to fifteen carbon atoms. Additionally, the alkynyl may be further substituted.

[0054] 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.

[0055] 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. The heteroaromatic ring group may be used interchangeably with heteroaryl. 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.

[0056] The term "aryl" refers to 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.

[0057] The term "heteroaryl" refers to 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, azaborane, borazine, 5λ 2 ,9λ 2 -diazab-13b-borata-anthra[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.

[0058] 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.

[0059] 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.

[0060] 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.

[0061] 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.

[0062] 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.

[0063] In other other cases, the most preferred general substituents are selected from the group consisting of deuterium, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0064] 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.

[0065] 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.

[0066] 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.

[0067] 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 entirety) describe the preparation of deuterium-substituted organometallic complexes. Further reference 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 entirety) respectively describe effective routes for the deuteration of methylene hydrogens in benzylamines and the replacement of aromatic ring hydrogens with deuterium.

[0068] 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 without valences fully occupied 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.

[0069] 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 attached fragments are considered equivalent.

[0070] 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 part of the ring formed by the pair of substituents is saturated and cases where part 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 next 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).

[0071] B. Compounds of the Present Disclosure

[0072] The present disclosure relates to organometallic complexes (e.g., Ir and Pt complexes) containing at least one ligand fused to indolo[3,2,1-jk]carbazole or a similar structure. The indolocarbazole-type moiety provides a stable polycyclic ring system capable of imparting narrow emission characteristics. In addition, elongation of the polycyclic ring system can lead to preferential molecular orientation in the thin film (e.g., alignment of transition dipole moments) to achieve higher efficiency in OLED devices.

[0073] In one aspect, the present disclosure provides a compound having a first ligand L A wherein the first ligand L A comprises a structure of Formula I:

[0074] In Formula I:

[0075] Each of moiety A and moiety B is independently a monocyclic or polycyclic fused ring system, wherein each ring in the monocyclic or polycyclic fused ring system is independently a 5- to 10-membered carbocyclic or heterocyclic ring;

[0076] The structure of Formula II: is fused to at least one of moiety A or moiety B through two or more adjacent ones of X 1 to X 11 ;

[0077] Each of Z 1 to Z 4 and X 1 to X 11 is independently C or N;

[0078] Each of L, Y A and Y B is independently 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';

[0079] Each of K 1 and K 2 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 );

[0080] Each of R A 、RB , R C1 , R C2 and R C3 each independently represents mono-substitution to the maximum allowable substitution, or no substitution;

[0081] Each R, R', R α , R β , R A , R B , R C1 , R C2 and R C3 is independently hydrogen or a substituent selected from the group consisting of general substituents defined herein;

[0082] L A is coordinated to a metal M having an atomic mass of at least 40;

[0083] The metal M can be coordinated with other ligands; and

[0084] L A can bind with other ligands to form a tridentate, tetradentate, pentadentate or hexadentate ligand.

[0085] In some embodiments, the compound is not selected from the group consisting of:

[0086]

[0087] In some embodiments, the first ligand L A has the structure of Formula I. In some embodiments, the first ligand L A consists essentially of the structure of Formula I.

[0088] In some embodiments, at least one R A , R B , R C1 , R C2 and R C3 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 C1 is selected from the group consisting of general substituents defined herein. In some embodiments, at least one R C2 is selected from the group consisting of general substituents defined herein. In some embodiments, at least one R C2 is selected from the group consisting of general substituents defined herein.

[0089] In some embodiments of Formula I, at least one Rα , R β , R, R', R A , R B , R C1 , R C2 and R C3 are 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 C1 is partially or fully deuterated. In some embodiments, at least one R C2 is partially or fully deuterated. In some embodiments, at least one R C3 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.

[0090] In some embodiments, each of part A and part B is independently a monocyclic or polycyclic fused ring system, wherein each ring in the monocyclic or polycyclic fused ring system is independently a 5 - membered or 6 - membered carbocyclic or heterocyclic ring. In some embodiments, each of part A and part B is independently an aryl or heteroaryl ring.

[0091] In some embodiments, at least one of part A or part B is a polycyclic fused ring system.

[0092] In some embodiments, at least one of part A or part B is a 5 - membered ring. In some embodiments, at least one of part A or part B is a 6 - membered ring.

[0093] In some embodiments, one of part A or part B is a polycyclic fused ring system, and the other of part A or part B is a 5 - membered ring. In some embodiments, one of part A or part B is a polycyclic fused ring system, and the other of part A or part B is a 6 - membered ring (e.g., benzene).

[0094] In some embodiments, each R, R', R α , R β , R A , R B , R C1 , R C2 and R C3 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 α , R β , R A , R B , R C1, R C2 and R C3 are 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 α , R β , R A , R B , R C1 , R C2 and R C3 are independently hydrogen or a substituent selected from the group consisting of most preferred general substituents as defined herein.

[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 selected from the group consisting of the following list of cyclic moieties: benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, imidazole-derived carbene, 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, benzimidazole-derived carbene, aza-benzimidazole-derived carbene, carbazole, aza-carbazole, dibenzofuran, aza-dibenzofuran, phenanthro[3,2-b]benzofuran, dibenzothiophene, aza-dibenzothiophene, quinoxaline, phthalazine, phenanthrene, aza-phenanthrene, anthracene, aza-anthracene, phenanthridine, fluorene, and aza-fluorene. In some embodiments, the aza variant includes one N on a benzo ring (e.g., which is a pyridine ring). In some embodiments, the aza variant includes one N on a benzo ring and the N is bonded to metal M.

[0097] In some embodiments, moiety A is monocyclic. In some embodiments, moiety A 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, moiety A is pyridine or imidazole. In some embodiments, moiety A is imidazole and forms an N-M bond. In some embodiments, moiety A is imidazole and forms a carbene-M bond.

[0098] In some embodiments, moiety A is a polycyclic fused-ring system. In some embodiments, moiety A 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, benzobenzimidazole, aza-benzobenzimidazole, benzimidazole-derived carbene, aza-benzimidazole-derived carbene, 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 A is quinoline, isoquinoline, or benzimidazole. In some embodiments, benzimidazole forms an N-M bond. In some embodiments, benzimidazole forms a carbene-M bond.

[0099] In some embodiments, moiety B is a monocyclic ring. In some embodiments, moiety B 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, moiety B is benzene.

[0100] In some embodiments, moiety B is a polycyclic fused-ring system. In some embodiments, moiety B 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, aza-benzimidazole, benzimidazole-derived carbene, aza-benzimidazole-derived carbene, 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 B is naphthalene, benzofuran, or dibenzofuran.

[0101] In some embodiments, each of moiety A and moiety B can independently be a polycyclic fused-ring structure. In some embodiments, each of moiety A and moiety B can independently be a polycyclic fused-ring structure comprising at least three fused rings. In some embodiments, the polycyclic fused-ring structure has two 6-membered rings and one 5-membered ring. In some such embodiments, the 5-membered ring is fused to the ring coordinated to metal M, and the second 6-membered ring is fused to the 5-membered ring. In some embodiments, each of moiety A and moiety B can independently be selected from the group consisting of dibenzofuran, dibenzothiophene, dibenzoselenophene, and their N-heterocyclic variants. In some such embodiments, each of moiety A and moiety B can be independently 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 N-heterocyclic variant contains exactly one N atom at the 6-position (ortho to O, S, or Se) and has a substituent at the 7-position (meta to O, S, or Se).

[0102] In some embodiments, each of moiety A and moiety B can independently be a polycyclic fused-ring structure comprising at least four fused rings. In some embodiments, the polycyclic fused-ring structure comprises three 6-membered rings and one 5-membered ring. In some such embodiments, the 5-membered ring is fused to the ring coordinated to 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.

[0103] In some embodiments, each of moiety A and moiety B can independently 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 the ring coordinated to metal M, the second 6-membered ring is fused to the 5-membered ring, the third 6-membered ring is fused to the second 6-membered ring, and the fourth 6-membered ring is fused to the third 6-membered ring.

[0104] In some embodiments, each of moiety A and moiety B can independently be an aza form of the polycyclic fused ring described above. In some such embodiments, each of moiety A and moiety B can independently contain exactly one aza N atom. In some such embodiments, each of moiety A and moiety B contains exactly two aza N atoms, and the two aza N atoms can be in one ring or in two different rings. In some such embodiments, the ring having an aza N atom is separated from the metal M atom by at least two other rings. In some such embodiments, the ring having an aza N atom is separated from the metal M atom by at least three other rings. In some such embodiments, each ortho position of the aza N atom is substituted.

[0105] In some embodiments, Z 1 is N or a carbene carbon and Z 4 is C. In some such embodiments, Z 1 is N. In some such embodiments, Z 1 is a carbene carbon.

[0106] In some embodiments, Z 2 and Z 3 are both C.

[0107] In some embodiments, Z 2 is N and Z 3 is C. In some such embodiments, Z 1 is a carbene carbon.

[0108] In some embodiments, K 1 is a direct bond.

[0109] 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 ).

[0110] In some embodiments, K 2 is a direct bond.

[0111] In some embodiments, K 2 is O or S. In some embodiments, K 2 is O. In some embodiments, K2 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 ).

[0112] In some embodiments, each of K 1 and K 2 is a direct bond.

[0113] In some embodiments, K 1 is a direct bond and K 2 is not a direct bond.

[0114] In some embodiments, L is a direct bond.

[0115] In some embodiments, L is selected from the group consisting of O, S, and Se.

[0116] In some embodiments, L is selected from the group consisting of BR, NR, and PR. In some embodiments, L is BR. In some embodiments, L is NR. In some embodiments, L is PR. In some of the foregoing embodiments, R is aryl or heteroaryl. In some such embodiments, R is joined or fused to one of R A or R B to form a ring. In some such embodiments, the ring is a 5-membered ring. In some such embodiments, the 5-membered ring is a pyrrole ring. In some such embodiments, the structure of Formula II is fused to the 5-membered ring. An example of such a ligand is

[0117] In some embodiments, L 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 is selected from the group consisting of: BRR', CRR', SiRR', and GeRR'. In some embodiments, L is CR.

[0118] In some embodiments, the structure of Formula II is directly fused to moiety A.

[0119] In some embodiments, the structure of Formula II is directly fused to moiety B.

[0120] In some embodiments, the structure of Formula II is indirectly fused to moiety A.

[0121] In some embodiments, the structure of Formula II is indirectly fused to moiety B. Examples of such ligands are

[0122] In some embodiments, the structure of Formula II is indirectly fused to moiety A and moiety B. Examples of such ligands are

[0123] In some embodiments, the structure of Formula II is fused to at least one of moiety A or moiety B through X 1 and X 2 either directly or indirectly. In some embodiments, the structure of Formula II is fused to at least one of moiety A or moiety B through X 2 and X 3 either directly or indirectly. In some embodiments, the structure of Formula II is fused to at least one of moiety A or moiety B through X 3 and X 4 either directly or indirectly. In some embodiments, the structure of Formula II is fused to at least one of moiety A or moiety B through X 5 and X 6 either directly or indirectly. In some embodiments, the structure of Formula II is fused to at least one of moiety A or moiety B through X 6 and X 7 either directly or indirectly. In some embodiments, the structure of Formula II is fused to at least one of moiety A or moiety B through X 8 and X 9 either directly or indirectly. In some embodiments, the structure of Formula II is fused to at least one of moiety A or moiety B through X 9 and X 10 either directly or indirectly. In some embodiments, the structure of Formula II is fused to at least one of moiety A or moiety B through X 10 and X 11 either directly or indirectly.

[0124] In some embodiments, Y A is a direct bond.

[0125] In some embodiments, Y A is selected from the group consisting of: O, S, and Se. In some embodiments, Y A is O. In some embodiments, Y A is selected from the group consisting of: BR, NR, and PR. In some embodiments, Y A 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, Y A is selected from the group consisting of: BRR', CRR', SiRR', and GeRR'. In some embodiments, YA is CR.

[0126] In some embodiments, Y B is a direct bond. In some embodiments, Y B is selected from the group consisting of: O, S, and Se. In some embodiments, Y B is O. In some embodiments, Y B is selected from the group consisting of: BR, NR, and PR. In some embodiments, Y B 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, Y B is selected from the group consisting of: BRR', CRR', SiRR', and GeRR'. In some embodiments, Y B is CR.

[0127] In some embodiments, Y A and Y B are the same. In some embodiments, Y A and Y B are both O. In some embodiments, Y A and Y B are both BR. In some embodiments, Y A and Y B are independently each one of C═O, C═S, C═Se, C═NR', or C═CRR'.

[0128] In some embodiments, Y A and Y B are different. In some embodiments, at least one of Y A or Y B is O. In some embodiments, at least one of Y A or Y B is BR. In some embodiments, at least one of Y A or Y B is C═O. In some embodiments, at least one of Y A or Y B is C═S, C═Se, C═NR', or C═CRR'.

[0129] In some embodiments, Y A and Y B are both direct bonds.

[0130] In some embodiments, each of X 1 to X 11 is C.

[0131] In some embodiments, X1 to X 11 at least one of which is N. In some embodiments, X 1 to X 11 exactly one of which is N.

[0132] In some embodiments, X 1 to X 4 each of which is C.

[0133] In some embodiments, X 1 to X 4 at least one of which is N. In some embodiments, X 1 to X 4 exactly one of which is N.

[0134] In some embodiments, X 5 to X 7 each of which is C.

[0135] In some embodiments, X 5 to X 7 at least one of which is N. In some embodiments, X 5 to X 7 exactly one of which is N.

[0136] In some embodiments, X 8 to X 11 each of which is C.

[0137] In some embodiments, X 8 to X 11 at least one of which is N. In some embodiments, X 8 to X 11 exactly one of which is N.

[0138] In some embodiments, the compound comprises an electron-withdrawing group. In some embodiments, the electron-withdrawing group has a Hammett constant greater than 0. In some embodiments, the electron-withdrawing group has a Hammett constant equal to or greater than 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0 or 1.1.

[0139] In some embodiments, the first ligand L Acomprising 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, cyano-containing alkyl, cyano-containing aryl, cyano-containing heteroaryl, isocyanate,

[0140]

[0141] wherein each R k1 represents mono-substitution to the maximum allowable substitution, or no substitution;

[0142] wherein 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

[0143] wherein R k1 、R k2 、R k3 、R e and R fEach of them is independently hydrogen or a substituent selected from the group consisting of the general substituents defined herein.

[0144] In some embodiments, the first ligand L A comprises an electron-withdrawing group selected from the group consisting of the structures in the following EWG2 list:

[0145]

[0146]

[0147] In some embodiments, the first ligand L A comprises an electron-withdrawing group selected from the group consisting of the structures in the following EWG3 list:

[0148]

[0149] In some embodiments, the first ligand L A comprises an electron-withdrawing group selected from the group consisting of the structures in the following EWG4 list:

[0150]

[0151] In some embodiments, the first ligand L A comprises an electron-withdrawing group, and the electron-withdrawing group is a π-electron-deficient electron-withdrawing group. In some embodiments, the π-electron-deficient electron-withdrawing group is selected from the group consisting of the structures in the following Pi-EWG list: CN, COCH3, CHO, COCF3, COOMe, COOCF3, NO2, SF3, SiF3, PF4, SF5, OCF3, SCF3, SeCF3, SOCF3, SeOCF3, SO2F, SO2CF3, SeO2CF3, OSeO2CF3, OCN, SCN, SeCN, NC, + N(R k2 )3, BR k2 R k3, 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,

[0152] wherein the variables are the same as those defined previously.

[0153] 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.

[0154] 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.

[0155] 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 Bis 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.

[0156] In some embodiments, at least one R C1 is or comprises an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R C1 is or comprises an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R C1 is or comprises an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R C1 is or comprises an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R C1 is or comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0157] In some embodiments, at least one R C2 is or comprises an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R C2 is or comprises an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R C2 is or comprises an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R C2 is or comprises an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R C2 is or comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0158] In some embodiments, at least one R C3 is or comprises an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R C3 is or comprises an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R C3 is or comprises an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R C3 is or comprises an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R C3 is or comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0159] In some embodiments, at least one R or R' is or comprises an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R or R' is or comprises an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R or R' is or comprises an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R or R' is or comprises an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R or R' is or comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0160] In some embodiments, at least one R A is not hydrogen. In some embodiments, at least one R A comprises at least one C atom. In some embodiments, at least one R A comprises a substituent selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0161] In some embodiments, at least one R B is not hydrogen. In some embodiments, at least one R B comprises at least one C atom. In some embodiments, at least one R B comprises a substituent selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0162] In some embodiments, at least one R C1 is not hydrogen. In some embodiments, Formula II is not bonded or fused directly or indirectly to moiety A or moiety B via X 1 to X 4 In some embodiments, R C1 is bonded to another ligand.

[0163] In some embodiments, at least one R C1 comprises at least one C atom. In some embodiments, at least one R C1 comprises a substituent selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0164] In some embodiments, two Rs C1 are joined or fused to form moiety C1, where moiety C1 is a monocyclic or polycyclic fused-ring system, and each ring in the monocyclic or polycyclic fused-ring system is independently a 5- to 10-membered carbocyclic or heterocyclic ring. In some embodiments, moiety C1 is selected from the group consisting of the list of cyclic moieties as defined herein. In some embodiments, moiety C1 is indole, which may be further substituted.

[0165] In some embodiments, at least one R C2 is not hydrogen. In some embodiments, Formula II is not bonded or fused to moiety A or moiety B directly or indirectly through X 5 to X 7 . In some embodiments, R C2 is bonded to another ligand.

[0166] In some embodiments, at least one R C2 contains at least one C atom. In some embodiments, at least one R C2 contains substituents selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0167] In some embodiments, two Rs C2 are joined or fused to form moiety C2, wherein moiety C2 is a monocyclic or polycyclic fused ring system, and each ring in the monocyclic or polycyclic fused ring system is independently a 5- to 10-membered carbocyclic or heterocyclic ring. In some embodiments, moiety C2 is selected from the group consisting of the list of cyclic moieties defined herein.

[0168] In some embodiments, at least one R C3 is not hydrogen. In some embodiments, Formula II is not bonded or fused to moiety A or moiety B directly or indirectly through X 8 to X 11 . In some embodiments, R C3 is bonded to another ligand.

[0169] In some embodiments, at least one R C3 contains at least one C atom. In some embodiments, at least one R C3 contains substituents selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0170] In some embodiments, two Rs C3 are joined or fused to form moiety C3, wherein moiety C3 is a monocyclic or polycyclic fused ring system, and each ring in the monocyclic or polycyclic fused ring system is independently a 5- to 10-membered carbocyclic or heterocyclic ring. In some embodiments, moiety C3 is selected from the group consisting of the list of cyclic moieties defined herein. In some embodiments, moiety C3 is indole, which may be further substituted.

[0171] In some embodiments, ligand L A is selected from the group consisting of the structures of List 1 below:

[0172]

[0173]

[0174]

[0175]

[0176] Wherein:

[0177] X 12 to X 25 are each independently C or N;

[0178] Z 5 , Z 6 and Z 7 are each 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';

[0179] When present, the ring containing Z 5 , Z 6 and Z 7 the dashed line in the ring indicates that the ring may be aromatic or non-aromatic;

[0180] Y C 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';

[0181] R C1 , R C2 , R C3 , R D and R E each independently represents a mono-substitution to the maximum allowable substitution, or no substitution;

[0182] Each R C1 , R C2 , R C3 , R D and R E is independently hydrogen or a substituent selected from the group of general substituents defined herein; and

[0183] any two substituents may optionally be joined or fused to form a ring.

[0184] In some embodiments, the ring containing Z 5 , Z 6 and Z 7 is an aromatic ring. In some embodiments, Z 5 , Z 6 and Z 7At least one of them is a heteroatom. In some embodiments, containing Z 5 , Z 6 and Z 7 The ring is imidazole.

[0185] In ligand L A In some embodiments selected from List 1, X 12 is C and is bonded to moiety A containing R A In some embodiments, X 13 is C and is bonded to moiety A containing R A In some embodiments, X 14 is C and is bonded to moiety A containing R A In some embodiments, X 15 is C and is bonded to moiety A containing R A In some embodiments, X

[0186] In ligand L A In some embodiments selected from List 1, at least one of R A , R C1 , R C2 , R C3 , R D and R E is selected from the group consisting of general substituents defined herein. In some embodiments, at least one of R A is selected from the group consisting of general substituents defined herein. In some embodiments, at least one of R C1 is selected from the group consisting of general substituents defined herein. In some embodiments, at least one of R C2 is selected from the group consisting of general substituents defined herein. In some embodiments, at least one of R C3 is selected from the group consisting of general substituents defined herein. In some embodiments, at least one of R D is selected from the group consisting of general substituents defined herein. In some embodiments, at least one of R E is selected from the group consisting of general substituents defined herein.

[0187] In ligand L A In some embodiments selected from List 1, at least one of R A , R C1 , R C2 , R C3 , R D and R E is partially or fully deuterated. In some embodiments, at least one of R A is partially or fully deuterated. In some embodiments, at least one of R D is partially or fully deuterated. In some embodiments, at least one of RC1 Partially or fully deuterated. In some embodiments, at least one R C2 Partially or fully deuterated. In some embodiments, at least one R C3 Partially or fully deuterated. In some embodiments, at least one R E Partially or fully deuterated. In some embodiments, at least one R or R' is partially or fully deuterated.

[0188] In ligand L A In some embodiments selected from List 1, 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.

[0189] In ligand L A In some embodiments selected from List 1, at least one R C1 is or comprises an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R C1 is or comprises an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R C1 is or comprises an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R C1 is or comprises an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R C1 is or comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0190] In ligand L A In some embodiments selected from List 1, at least one R C2 is or comprises an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R C2 is or comprises an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R C2 is or comprises an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R C2is or comprises an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R C2 is or comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0191] In some embodiments where ligand L A is selected from List 1, at least one R C3 is or comprises an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R C3 is or comprises an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R C3 is or comprises an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R C3 is or comprises an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R C3 is or comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0192] In some embodiments where ligand L A is selected from List 1, 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.

[0193] In some embodiments where ligand L A is selected from List 1, 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.

[0194] In some embodiments, ligand L A is selected from L A i-(Ri)(Rj)(Rk) a (Rl) a (Ym) b (Yn) b , where i is an integer from 1 to 54; when i is an integer from 1 to 48, a is 1 and b is 0; when i is an integer from 49 to 54, a is 0 and b is 1; each of Ym and Yn is independently selected from Y1 to Y7; each of Ri, Rj, Rk, and Rl is independently selected from R1 to R468, and L A 1-(R1)(R1)(R1)(R1) to L A 54-(R468)(R468)(Y7)(Y7) is defined in List 2 below:

[0195]

[0196]

[0197]

[0198]

[0199]

[0200]

[0201] where Y1 is O, Y2 is S, Y3 is CMe2, Y4 is SiPh2, Y5 is Y6 is and Y7 is C═O; and

[0202] where R1 to R468 have the structures defined in List 3 below:

[0203]

[0204]

[0205]

[0206]

[0207]

[0208]

[0209]

[0210]

[0211]

[0212]

[0213]

[0214]

[0215]

[0216]

[0217]

[0218]

[0219]

[0220]

[0221]

[0222]

[0223] 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 bidentate ligands; 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.

[0224] In some embodiments, L B comprises an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, L B comprises an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, L B comprises an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, L B comprises an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, L B comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0225] In some embodiments, LC 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.

[0226] 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 wherein L A , L B , and L C are different from each other.

[0227] In some embodiments, L B is a substituted or unsubstituted phenylpyridine, and L C is a substituted or unsubstituted acetylacetonate.

[0228] In some embodiments, the compound may have the formula Pt(L A )(L B ); and wherein L A and L B may be the same or different.

[0229] In some embodiments, L A is connected to L B to form a tetradentate ligand.

[0230] In some embodiments, L B and L C are each independently selected from the group consisting of the structures of List 4 below:

[0231]

[0232]

[0233]

[0234] Wherein:

[0235] T is selected from the group consisting of B, Al, Ga, and In;

[0236] K 1 ' 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 ;

[0237] Y 1 to Y 13 each independently is selected from the group consisting of C and N;

[0238] 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,

[0239] 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 ;

[0240] R e and R f may be fused or joined to form a ring;

[0241] Each R a , R b , R c and R d independently represents mono-substitution to the maximum allowable number of substitutions, or no substitution;

[0242] R a1 , R b1 , R c1 , R d1 , R a , R b , R c , R d , R e and R fEach of is independently hydrogen or a substituent selected from the group consisting of general substituents defined herein; and

[0243] R a1 , R b1 , R c1 , R d1 , R a , R b , R c and R d Any two substituents in may be fused or joined to form a ring or to form a multidentate ligand.

[0244] In some embodiments, L B and L C Each independently selected from the group consisting of the structures of Listing 5 below:

[0245]

[0246]

[0247]

[0248]

[0249]

[0250]

[0251] in:

[0252] R a' , R b' , R c' , R d' and R e' Each independently represents zero substitution, monosubstitution, or up to the maximum allowed number of substitutions on its associated ring;

[0253] R a '、R b '、R c '、R d ' and R e ' are each independently hydrogen or a substituent selected from the group consisting of general substituents defined herein; and

[0254] R a '、R b '、R c '、R d ' and R e The two substituents in ' may be fused or joined to form a ring or to form a multidentate ligand.

[0255] In some embodiments, LB Including structure: wherein the variables are the same as those defined previously. In some embodiments, Y 1 to Y 4 each independently is carbon. In some embodiments, Y 1 to Y 4 at least one of which is N. In some embodiments, Y 1 to Y 4 exactly one of which 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 germanium alkyl group. In some embodiments, at least one R a is a tertiary alkyl group. In some embodiments, Y 3 is C and the R a connected thereto is a tertiary alkyl group, a silyl group or a germanium alkyl 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 germanium alkyl 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 germanium alkyl group. In some embodiments, at least one R b is a tertiary alkyl group, a silyl group or a germanium alkyl group. In some embodiments, the tertiary alkyl group is tert-butyl. 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.

[0256] 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 ),

[0257] wherein LA According to any of the embodiments described herein, including L A 1-(R1)(R1)(R1)(R1) to L A 54-(R468)(R468)(Y7)(Y7);

[0258] where k is an integer from 1 to 530, and each L Bk has the structure defined in Listing 6 below:

[0259]

[0260]

[0261]

[0262]

[0263]

[0264]

[0265]

[0266]

[0267]

[0268]

[0269]

[0270]

[0271]

[0272] where each L Cj-I has a structure based on the following formula: and

[0273] each L Cj-II has a structure based on the following formula: where for each L Cj-I and L Cj-II in L Cj , R 201 and R 202 are defined in Listing 7 below:

[0274]

[0275]

[0276]

[0277]

[0278]

[0279]

[0280]

[0281]

[0282]

[0283]

[0284] wherein R D1 to R D246 has the structure defined in Listing 8 below:

[0285]

[0286]

[0287]

[0288] In some embodiments, the compound is selected from the group consisting of only those compounds of L Bk corresponding to one of the following: L B1 , L B30 , L B31 , L B109 , L B110 , L B112 , L B113 , L B114 , L B125 , L B127 , L B138 , L B140 , L B149 , L B150 , L B170 , L B171 , L B172 , L B174 , L B208 , L B241 , L B312 , L B315 , L B356 , L B367 , L B371, L B382 , L B439 , L B440 , L B455 , L B456 , L B457 , L B458 , L B461 , L B462 , L B463 , L B469 and L B476 .

[0289] In some embodiments, the compound is selected from the group consisting of only those compounds of L Bk corresponding to one of the following: L B1 , L B30 , L B31 , L B125 , L B138 , L B171 , L B172 , L B356 , L B357 , L B367 , L B371 , L B382 , L B455 and L B456 .

[0290] 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 one of the following structures: L Cj-I or L Cj-II ligand: R D1 , R D3 , R D4 , R D5 , R D9 , R D10 , R D17 , R D18 , R D20 , R D22 , R D37 , R D40 , R D41 , R D42 , R D43 , R D48 , R D49 , R D50 , R D54 , R D55 , R D58 , R D59 , R D78 , R D79 , R D81 , R D87 , RD88 , 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 .

[0291] In some embodiments, the compound is selected from the group consisting of compounds having only those ligands where the corresponding R 201 and R 202 are defined as being selected from one of the following structures: L Cj-I or L Cj-II : R D1 , R D3 , R D4 , R D5 , R D9 , R D10 , R D17 , R D22 , R D43 , R D50 , R D78 , R D116 , R D118 , R D133 , R D134 , R D135 , R D136, R D143 , R D144 , R D145 , R D146 , R D149 , R D151 , R D154 , R D155 , R D190 , R D193 , R D200 , R D201 , R D206 , R D210 , R D214 , R D215 , R D216 , R D218 , R D219 , R D220 , R D227 , R D237 , R D241 , R D242 , R D245 and R D246 .

[0292] In some embodiments, the compound is selected from the group consisting of compounds having only those L Cj-I ligands with one of the structures in Listing 9 below:

[0293]

[0294] In some embodiments, the compound has a formula selected from the group consisting of: Ir(L A )3, Ir(L A )2(L B ), Ir(L A )(L B )2, Ir(L A )2(L C ), and Ir(L A )(L B )(L C ). In some embodiments, L A is selected from the group consisting of the structures in Listing 1 and Listing 2, L B is selected from the group consisting of the structures in Listing 4, Listing 5, and Listing 6 (L Bk ), and L C is selected from the group consisting of the structures of L Cj-I and L Cj-II as defined herein.

[0295] In some embodiments, L A is selected from the group consisting of the structures in Listing 1, and LB Selected from the group consisting of L Bk 's structure. In some embodiments, L A is selected from the group consisting of the structures in List 2, and L B is selected from the group consisting of L Bk 's structure, where k is an integer from 1 to 530. In some embodiments, L A is selected from List 2 as defined herein, and L C is selected from the group consisting of L Cj-I and L Cj-II 's structure, where j is an integer from 1 to 1416.

[0296] In some embodiments, the compound may have the formula Ir(L A i-(Ri)(Rj)(Rk)(Rl)(Ym) V (Yn) W )3, which consists of compounds from Ir(L A 1-(R1)(R1)(R1)(R1))3 to Ir(L A 54-(R468)(R468)(Y7)(Y7))3; the formula Ir(L A i-(Ri)(Rj)(Rk)(Rl)(Ym) V (Yn) W )(L B )2; the formula Ir(L A i-(Ri)(Rj)(Rk)(Rl)(Ym) V (Yn) W )2(L B ); the formula Ir(L A )(L Bk )2; the formula Ir(L A )2(L Bk ); the formula Ir(L A i-(Ri)(Rj)(Rk)(Rl)(Ym) V (Yn) W )(L Bk )2, which consists of compounds from Ir(L A 1-(R1)(R1)(R1)(R1))(L B1 )2 to Ir(L A 54-(R468)(R468)(Y7)(Y7))(L B530 )2; the formula Ir(L A i-(Ri)(Rj)(Rk)(Rl)(Ym) V (Yn) W )2(L Bk ), which consists of Ir(LA 1-(R1)(R1)(R1)(R1))2(L B1 ) to Ir(L A 54-(R468)(R468)(Y7)(Y7))2(L B530 ) of the compound composition; formula Ir(L A i-(Ri)(Rj)(Rk)(Rl)(Ym) V (Yn) W )2(L Cj-I ) which is composed of Ir(L A 1-(R1)(R1)(R1)(R1))2(L C1-I ) to Ir(L A 54-(R468)(R468)(Y7)(Y7))2(L C1416-I ) of the compound composition; formula Ir(L A i-(Ri)(Rj)(Rk)(Rl)(Ym) V (Yn) W )2(L Cj-II ) which is composed of Ir(L A 1-(R1)(R1)(R1)(R1))2(L C1-II ) to Ir(L A 54-(R468)(R468)(Y7)(Y7))2(L C1416-II ) of the compound composition; formula Ir(L A i-(Ri)(Rj)(Rk)(Rl)(Ym) V (Yn) W )(L Bk )(L Cj-I ) which is composed of Ir(L A 1-(R1)(R1)(R1)(R1))(L B1 )(L C1-I ) to Ir(L A 54-(R468)(R468)(Y7)(Y7))(L B530 )(L C1416-I ) of the compound composition; or formula Ir(L A i-(Ri)(Rj)(Rk)(Rl)(Ym) V (Yn) W )(L Bk )(L Cj-II ) which is composed of Ir(L A 1-(R1)(R1)(R1)(R1))(L B1 )(L C1-II ) to Ir(L A54-(R468)(R468)(Y7)(Y7))(L B530 )(L C1416-II ) and is composed of compounds, where L A i-(Ri)(Rj)(Rk)(Rl)(Ym) V (Yn) W , L Bk and L Cj-I and L Cj-II are all defined herein.

[0297] In some embodiments, the compound is selected from the group consisting of the structures in List 10 below:

[0298]

[0299]

[0300]

[0301]

[0302]

[0303]

[0304]

[0305]

[0306]

[0307]

[0308]

[0309]

[0310]

[0311] In some embodiments, the compound comprises the structure of Formula III:

[0312] In Formula III:

[0313] M 1 is Pd or Pt;

[0314] Moieties E and F are each independently a monocyclic or polycyclic structure, where each ring in the monocyclic or polycyclic fused ring system is independently a 5- to 10-membered carbocyclic or heterocyclic ring;

[0315] Z3* and Z 4* are each independently C or N;

[0316] 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;

[0317] L 1 、L 2 and L 3 each independently do not exist or are 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', GeRR', alkylene, cycloalkyl, aryl, sub-cycloalkyl, sub-aryl, sub-heteroaryl, and combinations thereof, where at least one of L 1 and L 2 exists;

[0318] R E and R F each independently represent zero substitution, mono-substitution, or up to the maximum allowable number of substitutions;

[0319] R, R', R E and R F each independently is hydrogen or a substituent selected from the group consisting of the general substituents defined herein; and

[0320] where chemically feasible, two adjacent R A 、R B 、R C 、R E and R F can be joined or fused together to form a ring.

[0321] 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.

[0322] In some embodiments, portions E and F are each independently a monocyclic or polycyclic structure, where each ring in the monocyclic or polycyclic fused ring system is independently a 5-membered or 6-membered carbocyclic or heterocyclic ring.

[0323] In some embodiments of Formula III, at least one RA is selected from the group consisting of the general substituents defined herein. In some embodiments, at least one R B is selected from the group consisting of the general substituents defined herein. In some embodiments, at least one R C1 is selected from the group consisting of the general substituents defined herein. In some embodiments, at least one R C2 is selected from the group consisting of the general substituents defined herein. In some embodiments, at least one R C3 is selected from the group consisting of the general substituents defined herein. In some embodiments, at least one R E is selected from the group consisting of the general substituents defined herein. In some embodiments, at least one R F is selected from the group consisting of the general substituents defined herein.

[0324] In some embodiments of Formula III, at least one of R, R', R A , R B , 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 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, there is at least R or R' and is partially or fully deuterated.

[0325] In some embodiments of Formula III, at least one of R, R', R A , R B , R E or R F is or comprises an electron-withdrawing group from the EWG1 list defined herein. In some embodiments, at least one of R, R', R A , R B , R E or R F is or comprises an electron-withdrawing group from the EWG2 list defined herein. In some embodiments, at least one of R, R', R A , R B , R E or R F is or comprises an electron-withdrawing group from the EWG3 list defined herein. In some embodiments, at least one of R, R', R A , R B , R E or R Fis 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 E or R F is or comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0326] In some embodiments of Formula III, at least one of R A is or comprises an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one of R A is or comprises an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one of R A is or comprises an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one of R A is or comprises an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one of R A is or comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0327] In some embodiments of Formula III, at least one of R B is or comprises an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one of R B is or comprises an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one of R B is or comprises an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one of R B is or comprises an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one of R B is or comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0328] In some embodiments of Formula III, at least one of R E is or comprises an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one of R E is or comprises an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one of R E is or comprises an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one of R E is or comprises an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one of R E is or comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0329] 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.

[0330] 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.

[0331] In some embodiments of Formula III, both moiety E and moiety F are 6-membered aromatic rings.

[0332] In some embodiments of Formula III, moiety F is a 5- or 6-membered heteroaromatic ring.

[0333] In some embodiments of Formula III, L 1 is O or CRR'.

[0334] In some embodiments of Formula III, Z 4* is N and Z 3* is C. In some embodiments of Formula III, Z 4* is C and Z 3* is N.

[0335] In some embodiments of Formula III, L 2 is a direct bond. In some embodiments of Formula III, L 2 is NR.

[0336] 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, K 1 、K2 , K 3 and K 4 One of them is O.

[0337] In some embodiments of Formula III, the compound is selected from the group consisting of compounds having the formula Pt(L A' )(Ly):

[0338]

[0339] The ligand L A' is selected from L A' i'-(Lw)(Ro)(Rp)(Rq) c (Rr) c (Ym) d (Yn) d , where i' is an integer from 1 to 42; when i' is an integer from 1 to 21 or 28 to 42, c is 1 and d is 0; when i' is an integer from 22 to 27, c is 0 and d is 1; Lw is L1 or L2, where L1 is a direct bond and L2 is O; each of Ym and Yn is independently selected from Y1 to Y7; each of Ro, Rp, Rq, and Rr is independently selected from R1 to R468, and L A' 1-(L1)(R1)(R1)(R1)(R1) to L A' 42-(L2)(R468)(R468)(R468)(R468) is defined in the following List 11:

[0340]

[0341]

[0342]

[0343]

[0344]

[0345] where the ligand Ly is selected from Lyj-(Rs)(Rt)(Ru)(Rv), where j is an integer from 1 to 52; each of Rs, Rt, Ru, and Rv is independently selected from R1 to R468, and each of Ly1-(R1)(R1)(R1)(R1) to Ly1-(R468)(R468)(R468)(R468) is defined in the following List 12:

[0346]

[0347]

[0348]

[0349]

[0350]

[0351] wherein Y1 is O, Y2 is S, Y3 is CMe2, Y4 is SiPh2, Y5 is Y6 is and Y7 is C═O; and

[0352] wherein each of R1 to R468 has the structure defined in List 3 as defined herein.

[0353] In some embodiments, the compound is selected from the group consisting of the structures in the following List 13:

[0354]

[0355]

[0356]

[0357]

[0358]

[0359]

[0360]

[0361]

[0362]

[0363] In some embodiments, the first ligand L having the structure of Formula I described herein A of the compound can 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.

[0364] 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.

[0365] In some embodiments of the heteroleptic compound having the formula M(L A ) p (L B ) q (L C ) r the ligand L A has a first substituent R I , wherein 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 , wherein 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 , wherein 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 .

[0366] 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 value D D1 of the vector V 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 value D D2 of the vector V 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 value D D3 of the vector V 3 represents the straight-line distance between the metal M and the first atom a-III in the third substituent R III .

[0367] In such heteroleptic compounds, a sphere with radius r is defined, the center of which is the metal M and the radius r is the minimum radius allowing the sphere to enclose all atoms that are not part of the substituents R I 、R II and R III ; and wherein at least one of D 1 、D 2 and D 3 is at least In some embodiments, at least one of D 1 、D 2 and D 3 is at least 2.9, 3.0, 4.3, 4.4, 5.2, 5.9, 7.3, 8.8, 10.3, 13.1, 17.6 or In some embodiments, at least two of D 1 、D 2 and D 3 are at least 1.5, 2.9, 3.0, 4.3, 4.4, 5.2, 5.9, 7.3, 8.8, 10.3, 13.1, 17.6 or

[0368] 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 at least one of the angles between the transition dipole moment axis and the vectors V D1 、V D2 and V D3 is less than 40°. In some embodiments, at least one of the angles between the transition dipole moment axis and the vectors V D1 、V D2 and V D3 is less than 30°, 20°, 15° or 10°. In some embodiments, at least two of the angles between the transition dipole moment axis and the vectors V D1 、V D2 and V D3 are less than 20°. In some embodiments, at least two of the angles between the transition dipole moment axis and the vectors V D1 、V D2 and V D3 are less than 15° or 10°.

[0369] In some embodiments, all three angles between the transition dipole moment axis and the vectors V D1 、V D2 and V D3 are less than 20°. In some embodiments, the transition dipole moment axis and the vectors VD1 , V D2 and V D3 All three angles between and are less than 15° or 10°.

[0370] 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.

[0371] 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.

[0372] 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 other ligands. This also holds true 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 the case where the coordinated ligands are linked together, in some embodiments, all ligands can be the same, and in some other embodiments, at least one of the linked ligands can be different from the other ligands.

[0373] 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.

[0374] This disclosure encompasses any chemical structure that includes the novel compounds of this disclosure or their monovalent or polyvalent variants. In other words, the inventive compounds or their monovalent or polyvalent 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 "polyvalent 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 supramolecules, the inventive compounds can also be incorporated into supramolecular complexes without covalent bonds. 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 H or D atoms that may be attached to moiety B. This is because at least one H or D on the 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.

[0375] C. OLEDs and Devices of the Present Disclosure

[0376] 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.

[0377] In some embodiments, the OLED includes: an anode; a cathode; and an organic layer disposed between the anode and the cathode, where the organic layer includes a first ligand L having a structure of Formula I as disclosed herein A of the compound.

[0378] 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.

[0379] In some embodiments, the organic layer can further include a host, where 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-borata- naphtho[3,2,1-de]anthracene, azacyclohexaborane, oxaborole, dihydroacridine, xanthene, dihydrobenzoazasiline, dibenzooxasiline, phenoxazine, phenoxathiin, phenothiazine, dihydro- phenazine, 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-borata- naphtho[3,2,1-de]anthracene).

[0380] In some embodiments, the host may be selected from the group consisting of the structures in Host Group 1 below:

[0381]

[0382]

[0383]

[0384]

[0385]

[0386]

[0387]

[0388]

[0389]

[0390] Wherein:

[0391] Each of J1 to J6 is independently C or N;

[0392] L' is a direct bond or an organic linking group;

[0393] 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';

[0394] 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;

[0395] Each R, R', R A '、R B '、R C '、R D '、R E '、R F ' and R G ' are 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;

[0396] And, where possible, each unsubstituted aromatic carbon atom is optionally replaced by one or more N to form a nitrogen - substituted ring.

[0397] 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 are 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.

[0398] 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:

[0399]

[0400]

[0401] The structures of MG1 to MG27 are shown below:

[0402]

[0403]

[0404] 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.

[0405] 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 list of Group 2 of hosts, where each of MGb, EGa, and EGc is defined as follows:

[0406]

[0407]

[0408] 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.

[0409] In some embodiments, the organic layer may further comprise a host, wherein the host comprises a metal complex.

[0410] 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 an internal ferrocene-ferrocenium redox pair (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).

[0411] 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 excited state complex that serves 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, the acceptor, and the 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.

[0412] 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.

[0413] In some embodiments, the OLED can include additional compounds selected from the group consisting of: non-delayed fluorescent materials, delayed fluorescent materials, phosphorescent materials, and combinations thereof.

[0414] In some embodiments, the inventive compounds described herein are phosphorescent materials.

[0415] 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.

[0416] In some embodiments, the non-delayed fluorescence material or the delayed fluorescence material is an emitter that emits light within the OLED. In some embodiments, the non-delayed fluorescence material or the delayed fluorescence material does not emit light within the OLED. In some embodiments, the non-delayed fluorescence material or the delayed fluorescence material transfers its excited state energy to another material within the OLED. In some embodiments, the non-delayed fluorescence material or the delayed fluorescence material participates in charge transport within the OLED. In some embodiments, the non-delayed fluorescence material or the delayed fluorescence material is a receptor, and the OLED further includes a sensitizer.

[0417] In some embodiments of the OLED, the delayed fluorescence material includes 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 Pt, Pd, Zn, Cu, Ag, or Au complex (some of which are also referred to as metal-assisted (MA) TADF). In some embodiments, the metal-assisted delayed fluorescence material includes a metal-carbene bond. In some embodiments, the non-delayed fluorescence material or the delayed fluorescence 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 their combinations. In some embodiments, the non-delayed fluorescence material or the delayed fluorescence 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, perylene, phenanthrene, fluorene, pyrene, perylene and azulene.

[0418] In yet another aspect, the OLED of the present disclosure may further comprise an emission region containing a compound or a formulation of compounds as disclosed in the above compound portions of the present disclosure. In some embodiments, the emission region may comprise a compound or a formulation of compounds having a structure of Formula I as disclosed herein A of the ligand L. In some embodiments, the emission 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 emission 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 from 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.

[0419] 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, and the first OLED includes a first emissive region. The second sub-pixel includes a second OLED, and the second OLED includes 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.

[0420] 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, or 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, or 600 - 700 nm. In some embodiments, the first emissive region includes (if more than one) a first number of emissive layers deposited one on top of the other; and the second emissive region includes (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 include phosphorescent materials that can be the same or different. In some embodiments, the first emissive region includes a phosphorescent material, while the second emissive region includes a fluorescent material. In some embodiments, both the first emissive region and the second emissive region include fluorescent materials that can be the same or different.

[0421] In some embodiments, at least one pixel of the OLED or emission 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 emission region; and wherein the total number of emission regions within at least one pixel is equal to or less than N-1. In some embodiments, the second emission region is identical to the first emission region; and each sub-pixel of at least one pixel includes one emission region identical to the first emission 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 feature in the first pixel region is different from the corresponding display feature of the second pixel region, and wherein at least one display feature is selected from the group consisting of: resolution, cavity mode, color, out-coupling, and color filter.

[0422] 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 emission region disposed above the first electrode, a first CGL disposed above the first emission region, a second emission region disposed above the first CGL, and a second electrode disposed above the second emission region. In some embodiments, the first emission region and / or the second emission region may have various device features 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 emission regions in the pixelated OLED or stacked OLED include a sensitizer and a receptor having various sensitization device features and various embodiments of the inventive compounds disclosed herein. For example, the first emission region is included in the sensitization device while the second emission region is not included in the sensitization device; in some cases, both the first emission region and the second emission region are included in the sensitization device.

[0423] 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, 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, which non-radiatively couples to the emitter material and transfers the excited state energy from the emitter material to the non-radiative mode of surface plasmon polaritons. 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.

[0424] In some embodiments, the OLED further includes an out-coupling layer. In some embodiments, the out-coupling layer is disposed on the side opposite the organic emission layer above the enhancement layer. The out-coupling layer scatters the energy from the surface plasmon polaritons. 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.

[0425] 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, 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 OLEDs according to the present disclosure may further include any other functional layers common in OLEDs.

[0426] 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.

[0427] In some embodiments, the out-coupling layer has features of wavelength size or sub-wavelength size arranged periodically, quasi-periodically, or randomly. In some embodiments, the out-coupling layer may be composed of a plurality of nanoparticles. In some embodiments, the out-coupling layer is composed of a plurality of nanoparticles disposed above a material. In these embodiments, the out-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 from at least one of the following: metal, dielectric material, semiconductor material, metal alloy, mixture of dielectric materials, stack or layer of one or more materials, and / or a core of one type of material coated with a shell of another type of material. In some embodiments, the out-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 out-coupling layer is formed by lithography.

[0428] 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.

[0429] 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.

[0430] In some embodiments, a consumer product includes an OLED having an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer can include a first ligand L having a structure of Formula I disclosed herein A of a compound.

[0431] 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 electrode of opposite charge. 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 by 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.

[0432] 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.

[0433] Additional instances of each of these layers can be obtained. For example, flexible and transparent substrate-anode combinations are 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 at 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 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 at a molar ratio of 1:1, as disclosed in U.S. Patent Application Publication No. 2003 / 0230980, which is incorporated herein by reference in its entirety. U.S. Patents Nos. 5,703,436 and 5,707,745, which are incorporated herein by reference in their entirety, 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 blocking layers are described in more detail in U.S. Patent No. 6,097,147 and U.S. Patent Application Publication No. 2003 / 0230980, which are incorporated herein by reference in their entirety. Examples of injection layers 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.

[0434] Figure 2 Displays an inverted OLED 200. The device includes a substrate 210, a cathode 215, an emissive layer 220, a hole transport layer 225, and an anode 230. 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 device 200 has a cathode 215 disposed under the anode 230, device 200 can be referred to as an "inverted" OLED. Materials similar to those described with respect to device 100 can be used in the corresponding layers of device 200. Figure 2 Provides an example of how some of the layers can be omitted from the structure of device 100.

[0435] Figure 1 and 2The simple layered structure described herein is provided by way of non-limiting example, and it should be understood that embodiments of the present disclosure can be used in conjunction with a variety of other structures. The specific materials and structures described are exemplary in nature, and other materials and structures can be used. Functional OLEDs can be obtained by combining the various layers described in different ways, or the layers can be completely omitted based on design, performance, and cost factors. Other layers not specifically described can also be included. Materials other than those specifically described can 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 can be used, such as a mixture of a host and a dopant, or more generally, a mixture. Additionally, the layers can 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 the holes into emission layer 220, and can be described as a hole transport layer or a hole injection layer. In one embodiment, an OLED can be described as having an "organic layer" disposed between a cathode and an anode. This organic layer can comprise a single layer, or can further comprise multiple layers of different organic materials such as, for example, as described with respect to Figure 1 and 2 the different organic materials described.

[0436] Structures and materials not specifically described can also be used, such as OLEDs (PLEDs) comprising polymeric materials, 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 can be used. OLEDs can 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 can deviate from Figure 1 and 2 the simple layered structure described therein. For example, the substrate can include angled reflective surfaces 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 entireties.

[0437] 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 a particular deposition method. For example, substituents such as alkyl and aryl groups that are branched or unbranched and preferably contain at least 3 carbons 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 may 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.

[0438] 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 gas, etc. 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.

[0439] Devices manufactured 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 module can optionally include driving electronics and / or a power source. Devices manufactured 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, the OLED including a compound of the present disclosure in an organic layer of the OLED. The consumer product should include any kind of product that includes one or more light sources and / or one or more of certain types of visual displays. 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 with a diagonal less than 2 inches), 3-D displays, virtual reality or augmented reality displays, transportation vehicles, video walls that include multiple displays tiled together, theater or stadium screens, light therapy devices, and signs. A variety of control mechanisms can be used to control the devices manufactured in accordance with the present disclosure, including passive matrix and active matrix. It is intended that many of the devices 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 they can be used outside of this temperature range (e.g., from -40°C to +80°C).

[0440] 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.

[0441] 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.

[0442] In some embodiments, the OLED has one or more characteristics 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 can be in the emission layer or in other functional layers, such as a down-conversion layer.

[0443] 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 an illumination panel.

[0444] Other materials used in D.OLED

[0445] 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.

[0446] a) Conductive dopants:

[0447] 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.

[0448] b) HIL / HTL:

[0449] 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 generally 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; polymers containing fluorohydrocarbons; polymers having a conductive dopant; 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.

[0450] Examples of the aromatic amine derivatives for HIL or HTL include (but are not limited to) the following general structures:

[0451]

[0452] 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.

[0453] In some embodiments, each Ar 1 to Ar 9 independently comprises a moiety selected from the group consisting of:

[0454]

[0455] 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.

[0456] Examples of metal complexes used in HIL or HTL include, but are not limited to, the following general formula:

[0457] 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.

[0458] In some embodiments, (Y 101 -Y 102 ) is 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 0.6V compared to Fc + / Fc coupling.

[0459] In some embodiments, the HIL / HTL material is selected from the group consisting of: phthalocyanine and porphyrin compounds, starburst triarylamine, CF x fluorocarbon 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 semiconducting organic complexes, organometallic metal complexes, crosslinkable compounds, polythiophene-based polymers and copolymers, triarylamines, triarylamines containing spirofluorene cores, arylamine carbazole compounds, triarylamines containing (di)benzothiophene / (di)benzofuran, indolocarbazole, isoindole compounds and metal carbene complexes.

[0460] c) EBL:

[0461] 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 substantially higher efficiency and / or longer lifetime compared to similar devices 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.

[0462] d) Host:

[0463] 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.

[0464] Examples of metal complexes used as hosts preferably have the following general formula:

[0465]

[0466] 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.

[0467] In some embodiments, the metal complex is:

[0468]

[0469] where (O-N) is a bidentate ligand having a metal coordinated to the O and N atoms.

[0470] In some embodiments, Met is selected from Ir and Pt. In another embodiment, (Y 103 -Y 104 ) is a carbene ligand.

[0471] 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.

[0472] In some embodiments, the host compound contains at least one selected from the moieties consisting of the following:

[0473] 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.

[0474] In some embodiments, the host material is selected from the group consisting of arylcarbazole, metal 8-hydroxyquinolinates (e.g., alq3, balq), metal phenoxybenzothiazole compounds, conjugated oligomers and polymers (e.g., polyfluorene), aromatic fused rings, zinc complexes, based on Compounds, aryltriphenylene 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), tetracene 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, aza-carbazole / dibenzofuran / dibenzothiophene compounds, and high triplet metal organometallic complexes (e.g., metal-carbene complexes).

[0475] e) Emitter materials in the EML:

[0476] 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.

[0477] In some embodiments, the emitter material has the formula M(L 1 ) x (L 2 ) y (L 3 ) z ;

[0478] where L 1 , L 2 and L 3 can be the same or different;

[0479] where x is 1, 2, or 3;

[0480] where y is 0, 1, or 2;

[0481] where z is 0, 1, or 2;

[0482] where x + y + z is the oxidation state of the metal M;

[0483] where L 1 is selected from the group consisting of the structures in the following ligand list:

[0484]

[0485]

[0486]

[0487] wherein each L 2 and L 3 is independently selected from the group consisting of and the structures in the ligand list; wherein:

[0488] M is selected from the group consisting of: Ir, Rh, Re, Ru, Os, Pt, Pd, Zn, Au, Ag, and Cu;

[0489] T is selected from the group consisting of: B, Al, Ga, and In;

[0490] K 1 ' is a direct bond or is selected from the group consisting of NR e 、PR e 、O, S, and Se;

[0491] Each Y 1 to Y 15 is independently selected from the group consisting of carbon and nitrogen;

[0492] 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 ;

[0493] Each R a 、R b 、R c and R d can independently represent mono-substituted to the maximum possible number of substitutions or unsubstituted;

[0494] 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

[0495] Any two of these substituents may be fused or joined to form a ring or form a polydentate ligand.

[0496] In some embodiments, the emitter material is selected from the group consisting of dopant group 1:

[0497]

[0498]

[0499]

[0500]

[0501] wherein

[0502] X 96 to X 99 each independently is C or N;

[0503] each Y 100 is independently selected from the group consisting of NR″, O, S, and Se;

[0504] R 10a , R 20a , R 30a , R 40a and R 50a each independently represents mono-substituted, up to maximally substituted, or unsubstituted;

[0505] 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 of general substituents defined herein; any two substituents may be joined or fused to form a ring.

[0506] In some embodiments, the emitter material is selected from the group consisting of dopant group 2:

[0507]

[0508]

[0509]

[0510]

[0511]

[0512] Wherein:

[0513] Each Y 100 is independently selected from the group consisting of NR″, O, S, and Se;

[0514] 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;

[0515] X 100 and X 200 each occurrence is independently selected from the group consisting of O, S, Se, NR″, and CR″R″′;

[0516] Each R A ″, R B ″, R C ″, R D ″, R E ″, R F ″ independently represents mono-substituted, up to maximum substitution, or unsubstituted;

[0517] 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 of general substituents as defined herein; any two substituents may be joined or fused to form a ring.

[0518] In some embodiments of the above dopant groups 1 and 2, each unsubstituted aromatic carbon atom can 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 can be replaced by a Pd atom.

[0519] 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.

[0520] 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, L 5 and L 6 are different, and L 5 and L 6 are independently selected from the group consisting of:

[0521]

[0522] where A 1 -A 9 are each independently selected from C or N;

[0523] each R P , R Q and R U independently represents mono-substituted, up to maximum substitution or unsubstituted;

[0524] 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; and any two substituents can be joined or fused to form a ring.

[0525] In some embodiments of the OLED, the delayed fluorescence material comprises at least one selected from the group consisting of donor moieties:

[0526]

[0527] where YT , Y U , Y V and Y W are each independently selected from the group consisting of: B, C, Si, Ge, N, P, O, S, Se, C═O, S═O, and SO2.

[0528] 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.

[0529] 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 atoms).

[0530] In some embodiments, the fluorescent material comprises at least one selected from the group consisting of chemical moieties:

[0531]

[0532]

[0533] wherein Y F , Y G , Y H and Y I are each independently selected from the group consisting of: B, C, Si, Ge, N, P, O, S, Se, C═O, S═O, and SO2;

[0534] wherein X F and X G are each independently selected from the group consisting of C and N.

[0535] 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.

[0536] f) HBL:

[0537] 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. Additionally, 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 higher triplet energy compared to one or more of the emitters closest to the HBL interface.

[0538] 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.

[0539] In some embodiments, the compound used in the HBL comprises at least one of the following moieties selected from the group consisting of:

[0540]

[0541] where k is an integer from 1 to 20; L 101 is another ligand, and k' is an integer from 1 to 3.

[0542] g) ETL:

[0543] The electron transport layer (ETL) can include materials 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.

[0544] In some embodiments, the compound used in the ETL contains at least one of the following moieties in the molecule:

[0545] 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.

[0546] In some embodiments, the metal complex used in the ETL contains, but is not limited to, the following general formula:

[0547]

[0548] where (O-N) or (N-N) is a bidentate ligand having a metal coordinated to the 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.

[0549] 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.

[0550] h) Charge - generating layer (CGL)

[0551] 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.

[0552] In any of the compounds disclosed herein, the hydrogen atoms may 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.

[0553] 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 may be replaced with other materials and structures without departing from the spirit of the invention. The invention as claimed may 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.

[0554] E. Experimental data

[0555]

[0556] Synthesis of Ligand 1

[0557] A solution of potassium carbonate (8.63 g, 62.5 mmol, 2.0 equiv) in water (30 mL) was added to a solution of (3-chloro-2-hydroxyphenyl)boronic acid (5.92 g, 34.4 mmol, 1.1 equiv) and 2-bromoindolo[3,2,1-jk]carbazole (10.0 g, 31.2 mmol, 1.0 equiv) in ethanol (30 mL) and toluene (30 mL), and the mixture was bubbled with nitrogen for 5 minutes.

[0558] Tetrakis(triphenylphosphine)palladium(0) (1.81 g, 1.56 mmol, 0.05 equiv) was added, and the mixture was heated at 100 °C overnight. The reaction mixture was cooled to room temperature and diluted with ethyl acetate (200 mL) and water (200 mL). The layers were separated, and the aqueous layer was washed with dichloromethane (3 × 100 mL). The combined organic layers were concentrated, adsorbed onto silica gel (80 g) and purified on silica gel using dichloromethane and hexane to give 2-chloro-6-(indolo[3,2,1-jk]carbazol-2-yl)phenol (6.0 g, 52% yield) as a white solid.

[0559] A mixture of 2-chloro-6-(indolo[3,2,1-jk]carbazol-2-yl)phenol (5.66 g, 15.4 mmol, 1.0 equiv), palladium(II) acetate (0.173 g, 0.769 mmol, 0.05 equiv), 1,3-bis(2,6-diisopropylphenyl)imidazolium chloride (0.654 g, 1.54 mmol, 0.1 equiv), 5H-cyclopenta[2,1-b:3,4-b']dipyridin-5-one (0.280 g, 1.54 mmol, 0.1 equiv), potassium carbonate (4.25 g, 30.8 mmol, 2.0 equiv), 2,4,6-trimethylbenzoic acid sodium salt (1.43 g, 7.69 mmol, 0.5 equiv), activated molecular sieve 4 Å (0.6 g) and mesitylene (85 mL) was bubbled with nitrogen for 10 minutes. The reaction mixture was heated at 140 °C in air for 6 days. The reaction mixture was cooled to room temperature, diluted with dichloromethane (500 mL) and filtered. The solid was washed with dichloromethane (300 mL) and the combined filtrates were concentrated under reduced pressure to a volume of 85 mL, and then purified on silica gel using dichloromethane and hexane to give 14-chlorobenzo[f]indolo[1,2,3-lm]carbazole (1.1 g, 20% yield) as an off-white solid.

[0560] A mixture of potassium acetate (1.07 g, 10.9 mmol, 4.0 equiv) was added to a solution of 14-chlorobenzofuro[2,3-b]indolo[1,2,3-lm]carbazole (1.00 g, 2.734 mmol, 1.0 equiv) and 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bis(1,3,2-dioxaborolane) (1.39 g, 5.47 mmol, 2.0 equiv) in 1,4-dioxane (100 mL), and the solution was bubbled with nitrogen for 5 min. XPhosPd-G2 (0.215 g, 0.273 mmol, 0.1 equiv) was added, and bubbling was continued for another 5 min, and the mixture was heated at 120 °C for 24 h. The mixture was cooled to room temperature, diluted with dichloromethane (400 mL) and passed through a pad of diatomaceous earth (30 g), which was rinsed with dichloromethane (100 mL). The filtrate was concentrated under reduced pressure to give 14-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzofuro[2,3-b]indolo[1,2,3-lm]carbazole (3.14 g) as a black viscous oil.

[0561] A solution of potassium carbonate (3.80 g, 27.5 mmol, 4.0 equiv) in water (10 mL) was added to a solution of 14-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzofuro[2,3-b]indolo[1,2,3-lm]carbazole (3.14 g, 6.87 mmol, 1.0 equiv) and 2-chloro-4-(2,2-dimethylpropyl-1,1-d2)-5-(methyl-d3)pyridine (2.51 g, 12.4 mmol, 1.8 equiv) in 1,4-dioxane (60 mL), and the mixture was bubbled with nitrogen for 5 min. Tetrakis(triphenylphosphine)palladium(0) (0.793 g, 0.687 mmol, 0.1 equiv) was added, and bubbling was continued for another 5 min, and the mixture was heated at 110 °C. The reaction mixture was cooled to room temperature and diluted with dichloromethane (500 mL) and water (200 mL). The layers were separated, and the aqueous layer was washed with dichloromethane (3 × 100 mL). The combined organic layers were concentrated to dryness. The residue was redissolved in dichloromethane (500 mL) and then concentrated to about 80 mL. It was then purified on silica gel using dichloromethane and ethyl acetate to give ligand 1 (1.1 g, 32% yield) as a white solid.

[0562]

[0563] Synthesis of Emitter 1

[0564] Charge a 100 mL vial equipped with a stir bar with ligand 1 (0.600 g, 1 Eq, 1.21 mmol), dimer 1 (1.41 g, 1.5 Eq, 1.81 mmol), and acetone (40.2 mL). Bubble the mixture with nitrogen for 10 minutes, then add triethylamine (610 mg, 0.840 mL, 5.00 Eq, 6.03 mmol). Reflux the system under an inert atmosphere for 16 hours. Dilute the mixture in THF and perform photoisomerization. Concentrate the solvent in vacuo. Grind the crude product with approximately 50 mL of dichloromethane / methanol (1:10 v / v) at 40 °C for 1 hour and filter. Wash the residue additionally with methanol (approx. 15 mL) to obtain emitter 1 (1 g, 78% yield).

[0565]

[0566] Synthesis of emitter 2

[0567] Charge a 40 mL vial equipped with a stir bar with ligand 1 (0.100 g, 1 Eq, 201 μmol), dimer 2 (260 mg, 1.5 Eq, 301 μmol), and acetone (6.70 mL). Bubble the mixture with nitrogen for 10 minutes, then add triethylamine (102 mg, 140 μL, 5.0 Eq, 1.00 mmol). Reflux the system under an inert atmosphere for 16 hours. Dilute the mixture in THF and perform photoisomerization. After photoisomerization, concentrate the solution in vacuo and grind with 20 mL of dichloromethane / methanol (1:10 v / v) and heat at 40 °C for 1 hour. Filter the solid and wash with methanol (approx. 5 mL).

[0568] Wash the residue additionally with methanol (5 mL) and dry in vacuo at 40 °C to obtain emitter 2 (143 mg, 61% yield).

[0569]

[0570] Synthesis of emitter 3

[0571] A 40 mL vial equipped with a stir bar was charged with ligand 1 (100.0 mg, 1 Eq, 200.9 μmol), dimer 3 (259.8 mg, 1.5 Eq, 301.4 μmol), and acetone (6.698 mL). The mixture was bubbled with nitrogen for 10 minutes, followed by the addition of triethylamine (101.7 mg, 140 μL, 5.0 Eq, 1.005 mmol). The system was refluxed under an inert atmosphere for 16 hours. The mixture was diluted in THF and subjected to photoisomerization. After photoisomerization, the solution was concentrated in vacuo and triturated with 20 mL of dichloromethane / methanol (1:10 v / v) and heated at 40 °C for 1 hour. The solid was filtered and washed with methanol (ca. 5 mL). The residue was further washed with methanol (5 mL) and dried in vacuo at 40 °C to afford emitter 3 (127 mg, 55% yield).

[0572] Comparative Example 1:

[0573]

[0574] The emission spectra of emitter 1, emitter 2, emitter 3, and Comparative Example 1 were all measured and are shown in Table 1. The emission spectra were obtained from 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. λmax is the peak maximum of these emission spectra and FWHM is the full width at half maximum of these emission spectra. All samples were excited at 340 nm.

[0575] Table 1: Comparison of PL emission spectra in 2meTHF at room temperature

[0576] Emitter λmax (nm) FWHM (nm) Emitter 1 524 nm 61 nm Emitter 2 518 nm 61 nm Emitter 3 517 nm 57 nm Comparative Example 1 569 nm 75 nm

[0577] As can be seen in Table 1, each of emitters 1 to 3 has a blue-shifted emission spectrum and a narrower FWHM compared to the comparative compounds with directly metallated indolocarbazoles. These increases exceed any values attributable to experimental error, and the observed improvements are significant and unexpected.

[0578] The optoelectronic properties of the compounds of the present invention listed in Table 2 were calculated. Calculations were performed using the B3LYP functional with a 6-31G* basis set. Geometric optimizations were carried out in vacuo. The excitation energies were obtained using time-dependent density functional theory (TDDFT) at these optimized geometries. A continuum solvent model was applied in the TDDFT calculations to simulate the tetrahydrofuran solvent. All calculations were performed using the Gaussian program.

[0579] The calculations obtained with the above DFT functional sets and basis sets are theoretical. Computational composite protocols, such as the Gaussian protocol with the 6-31G* basis set (or the CEP-31G basis set applicable to organometallic molecules) used herein, rely on the assumption that electronic effects are additive, and thus, larger basis sets can be used to extrapolate to the complete basis set (CBS) limit. However, when the research objective is to understand the variations in HOMO, LUMO, S1, T1, bond dissociation energies, etc. of a series of structurally related compounds, 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 experiments well. See, for example, Hong et al., Chem. Mater. 2016, 28, 5791-98, 5792-93 and Supplementary Information (discussing the reliability of DFT calculation results in the case of OLED materials). In addition, 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 of various emissive complexes); G. R. Morello, J. Mol. Model. 2017, 23:174 (studying various DFT functional sets and basis sets and inferring that the combination of B3LYP and CEP-31G is particularly accurate for emissive complexes).

[0580]

[0581]

[0582]

[0583] The compounds of the present invention in Table 2 all exhibit green to yellow T1 energies and, due to their similarity to emitters 1 to 3, are expected to exhibit a narrower emission spectrum.

Claims

1. A method having a first ligand L A The compound, the first ligand L A The structure comprising Formula I: in: Each of moiety A and moiety B is independently a monocyclic or polycyclic fused ring system, wherein each ring in the monocyclic or polycyclic fused ring system is independently a 5- to 10-membered carbocyclic or heterocyclic ring; The structure of formula II By X 1 To X 11 Two or more neighbors of are fused to at least one of portion A or portion B; Z 1 to Z 4 and X 1 To X 11 Each of is independently C or N; L, Y A and Y B Each of which is independently 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' and GeRR'; K 1 and K 2 Each 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 C1 , R C2 and R C3 Each independently represents mono-substitution to the maximum permissible substitution, or no substitution; Each R, R', R α , R β , R A , R B , R C1 , R C2 and R C3 are independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, germanyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thiol, sulfinyl, sulfonyl, phosphino, selenanyl, and combinations thereof; L A coordinated to a metal M having an atomic mass of at least 40; The metal M can be coordinated with other ligands; as well as L A Can be joined with other ligands to form a tridentate, tetradentate, pentadentate or hexadentate ligand, provided that the compound is not selected from the group consisting of:

2. The compound of claim 1, wherein each of moiety A and moiety B is independently selected from the group consisting of the following cyclic moieties: benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, imidazole-derived carbenes, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole, triazole, naphthalene, quinoline, isoquinoline, quinazoline, benzofuran, aza-benzofuran, phenanthro[3,2-b]benzofuran, benzoxazole, aza-benzoxazole, benzothiophene, aza-benzothiophene, benzothiazole, aza-benzothiazole, benzoselenophene, aza-benzoselenophene, indene, aza-indene, indole, aza-indole, benzimidazole, aza-benzimidazole, benzimidazole, aza-benzimidazole, benzimidazole-derived carbene, aza-benzimidazole-derived carbene, 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 is N or carbene carbon and Z 4 is C; and / or wherein Z 2 and Z 3 All C or Z 2 N and Z 3 is C; and / or K 1 is a direct bond, O or S; and / or wherein K 2 is a direct bond, O or S; and / or wherein L is a direct bond; and / or wherein the structure of Formula II is directly fused to part A or part B; and / or wherein Y A is a direct bond, O, S, BR, CRR', SiRR', CRR', SiRR' or C=O; and / or wherein Y B is a direct bond, O, S, BR, CRR', SiRR', CRR', SiRR' or C=O; and / or wherein Y A and Y B The same; and / or where X 1 To X 11 Each of C or X 1 To X 11 At least one of them is N.

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 C1 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 C2 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 C3 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 the first ligand L A comprising an electron withdrawing group selected from the group consisting of: 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 dibenzoborole, 1-substituted carbazole, 1,9-substituted carbazole, substituted or unsubstituted carbazole, substituted or unsubstituted pyridine, substituted or unsubstituted pyrimidine, substituted or unsubstituted pyrazine, substituted or unsubstituted pyridoxine, substituted or unsubstituted triazine, substituted or unsubstituted oxazole, substituted or unsubstituted benzoxazole, substituted or unsubstituted thiazole, substituted or unsubstituted benzothiazole, substituted or unsubstituted imidazole, substituted or unsubstituted benzimidazole, ketone, carboxylic acid, ester, nitrile, isonitrile, sulfinyl, sulfonyl, partially and fully fluorinated alkyl, partially and fully fluorinated aryl, partially and fully fluorinated heteroaryl, cyano-containing alkyl, cyano-containing aryl, cyano-containing heteroaryl, isocyanate, Each R k1 indicates mono-substitution to the maximum permissible substitution, or no substitution; where Y G Select 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 ;as well as Where R k1 , R k2 , R k3 , R e and R f Each of the above is independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, germanyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thiol, selenanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

5. The compound according to claim 1, wherein two R C1 are joined or fused to form a moiety C1, wherein the moiety C1 is a monocyclic or polycyclic fused ring system, wherein each ring in the monocyclic or polycyclic fused ring system is independently a 5- to 10-membered carbocyclic or heterocyclic ring; and / or wherein two R C2 are joined or fused to form a moiety C2, wherein the moiety C2 is a monocyclic or polycyclic fused ring system, wherein each ring in the monocyclic or polycyclic fused ring system is independently a 5- to 10-membered carbocyclic or heterocyclic ring; and / or wherein two R C3 joined or fused to form moiety C3, wherein moiety C3 is a monocyclic or polycyclic fused ring system, wherein each ring in the monocyclic or polycyclic fused ring system is independently a 5- to 10-membered carbocyclic or heterocyclic ring; and / or wherein the metal M is selected from the group consisting of Ir, Rh, Re, Ru, Os, Pt, Pd, Ag, Au, and Cu.

6. The compound according to claim 1, wherein the ligand L A Select from the group consisting of: in: X 12 To X 25 each independently is C or N; Z 5 , Z 6 and Z 7 Each 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'; When present, contains Z 5 , Z 6 and Z 7 The dashed lines in the rings of indicate that the rings may be aromatic or non-aromatic; Y C 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'; R C1 , R C2 , R C3 , R D and R E Each independently represents mono-substitution to the maximum permissible substitution, or no substitution; Each R C1 , R C2 , R C3 , R D and R E is independently hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, germanyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thiol, sulfinyl, sulfonyl, phosphino, selenanyl, 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) a (Rl) a (Ym) b (Yn) b , wherein i is an integer from 1 to 54; when i is an integer from 1 to 48, a is 1 and b is 0; when i is an integer from 49 to 54, a is 0 and b is 1; each of Ym and Yn is independently selected from Y1 to Y7; each of Ri, Rj, Rk and Rl is independently selected from R1 to R468, and L A 1-(R1)(R1)(R1)(R1) to L A Each of 54-(R468)(R468)(Y7)(Y7) is defined as follows: Wherein Y1 is O, Y2 is S, Y3 is CMe2, Y4 is SiPh2, Y5 is Y6 and Y7 is C═O; and Wherein R1 to R468 have the structure defined as follows:

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 having the 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 which 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 monosubstitution 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, halide, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, germanyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thiol, selenanyl, 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 substituents in 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 530, and each L Bk Has the structure defined as follows: Each L Cj-I Has a structure based on the following formula: as well as Each L Cj-II Has a structure based on the following formula: For L Cj-I and L Cj-II Each L Cj , R 201 and R 202 The definition is as follows: Where R D1 to R D246 Has the structure defined as follows:

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, wherein each ring in the monocyclic or polycyclic fused ring system is independently 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 them exists; R E and R F each independently represents zero substitution, monosubstitution, or up to the maximum allowed number of substitutions; R, R', R E and R F Each of is independently hydrogen or a substituent selected from the group consisting of: deuterium, halide, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, germanyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, selenoanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; as well as When chemically feasible, two adjacent R A , R B , R C , R E and R F May be joined or fused together to form a ring.

14. An organic light-emitting device, comprising: anode; a 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; a 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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