Organic electroluminescent materials and devices

Abstract

To provide organic or metal coordination compounds and formulations having excellent properties, and various uses thereof as light emitters, sensitizers, charge transporters or exciton transporters in devices such as organic light emitting diodes and related electronic devices and consumer products.SOLUTION: A compound having a first ligand LA, wherein the ligand LA comprises a structure of the formula: wherein LA is coordinated to a metal M, wherein M is Ir, Rh, Re, Ru, Os, Pt, or the like.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application is a continuation-in-part of co-pending U.S. patent application Ser. No. 18 / 814,301, filed Aug. 23, 2024; Ser. No. 19 / 176,025, filed Apr. 10, 2025; and Ser. No. 18 / 814,299, filed Aug. 23, 2024. This application also claims priority under 35 U.S.C. §119(e) to U.S. Provisional Application No. 63 / 738,566, filed December 24, 2024, U.S. Provisional Application No. 63 / 795,731, filed April 28, 2025, U.S. Provisional Application No. 63 / 742,057, filed January 6, 2025, U.S. Provisional Application No. 63 / 678,268, filed August 1, 2024, U.S. Provisional Application No. 63 / 754,002, filed February 5, 2025, and U.S. Provisional Application No. 63 / 793,115, filed April 23, 2025, the entire contents of which are incorporated herein by reference.

[0002] The present disclosure relates generally to organic or metal coordination compounds and formulations and their various uses as emitters, sensitizers, charge transporters or exciton transporters in devices such as organic light emitting diodes and related electronic devices and consumer products.

[0003] Optoelectronic devices that utilize organic materials are becoming increasingly desirable for a variety of reasons. Because many of the materials used to fabricate such devices are relatively inexpensive, organic optoelectronic devices have the potential for cost advantages over inorganic devices. In addition, the inherent properties of organic materials, such as flexibility, may make them well suited for specific applications, such as fabrication on flexible substrates. Examples of organic optoelectronic devices include organic light-emitting diodes / devices (OLEDs), organic phototransistors, organic photovoltaic cells, organic scintillators, and organic photodetectors. For OLEDs, organic materials may have performance advantages over conventional materials.

[0004] OLEDs utilize thin organic films that emit light when a voltage is applied across the device, and are becoming an increasingly interesting technology for use in applications such as displays, lighting, and backlighting.

[0005] One application of emissive molecules is full-color displays. Industry standards for such displays require pixels adapted to emit specific colors, referred to as "saturated" colors. In particular, these standards require saturated red, green, and blue pixels. Alternatively, OLEDs can be designed to emit white light. Conventional liquid crystal display emission from a white backlight is filtered with absorption filters to produce red, green, and blue emission. Similar techniques can be used with OLEDs. White OLEDs can be either single-emissive-layer (EML) devices or stack structures. Color can be measured using CIE coordinates, which are well known in the art. Summary of the Invention

[0006] In one aspect, the present disclosure provides a compound comprising a first ligand L A wherein the first ligand L A has the structure of Formula I: [ka] (In the formula, Moieties A and D are each independently a monocyclic ring or a polycyclic fused ring system, and each ring of the monocyclic ring or polycyclic fused ring system is independently a 5- to 10-membered carbocyclic or heterocyclic ring; The moiety C is a 5- or 6-membered carbocyclic or heterocyclic ring; Z 1 , Z 2 and X 1 ~X 4 each is independently C or N; Part A is X 1 ~X 4 and binds to one of the X 1 ~X 4One of them is C; Y is selected from the group consisting of BR, BRR', NR, PR, P(O)R, O, S, Se, C=O, C=S, C=Se, C=NR', C=CRR', S=O, SO2, CR, CRR', SiRR', and GeRR'; K is 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 ) selected from the group consisting of; R A , R B , R C , and R D each independently represents one to the maximum number of substitutions or no substitutions; Each R, R', R α , R β , R A , R B , R C , and R D is independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boryl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, selenyl, and combinations thereof; At least one R C or R D is a substituent R containing a carbocyclic or heterocyclic group * ) L A is coordinated to the metal M; M is selected from the group consisting of Ir, Rh, Re, Ru, Os, Pt, Pd, Ag, Au, and Cu; M may be coordinated to other ligands; L Amay, in combination with other ligands, comprise a tridentate, tetradentate, pentadentate, or hexadentate ligand; and Any two substituents may be joined or fused to form a ring, to provide a compound.

[0007] In another aspect, the present disclosure provides a first ligand L described herein. A The present invention provides a formulation of a compound having the formula:

[0008] In yet another aspect, the present disclosure provides a compound comprising a first ligand L described herein. A The present invention provides an OLED having an organic layer comprising a compound having the formula:

[0009] In yet another aspect, the present disclosure provides a compound comprising a first ligand L described herein. A The present invention provides a consumer product comprising an OLED having an organic layer comprising a compound having the formula: [Brief explanation of the drawings]

[0010] [Figure 1] FIG. 1 shows an organic light-emitting device.

[0011] [Figure 2] FIG. 2 shows an inverted organic light emitting device that does not have a separate electron transport layer. DETAILED DESCRIPTION OF THE INVENTION

[0012] A. Terminology Unless otherwise stated, the following terms used herein are defined as follows:

[0013] As used herein, "top" means furthest from the substrate, while "bottom" means closest to the substrate. When a first layer is described as "disposed over" a second layer, the first layer is disposed further from the substrate. There may be other layers between the first and second layers, unless it is specified that the first layer is "in contact with" the second layer. For example, a cathode may be described as "disposed over" an anode, even though there may be various organic layers in between.

[0014] As used herein, "solution processable" means capable of being dissolved, dispersed or transported in and / or deposited from a liquid medium, either in the form of a solution or suspension.

[0015] As used herein, and as generally understood by those skilled in the art, a 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 if the first energy level is closer to the vacuum energy level. Because ionization potentials (IPs) are measured as negative energies relative to the vacuum level, a higher HOMO energy level corresponds to an IP having a smaller absolute value (a less negative IP). Similarly, a higher LUMO energy level corresponds to an electron affinity (EA) having a smaller absolute value (a less negative EA). On a conventional energy level diagram, with the vacuum level at the top, 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 such a diagram than a "lower" HOMO or LUMO energy level.

[0016] As used herein, and as generally understood by those skilled in the art, a first work function is "greater than" or "higher than" a second work function if the first work function has a higher absolute value. Because work functions are generally measured as negative numbers relative to vacuum level, this means that a "higher" work function is more negative. On a conventional energy level diagram, with the vacuum level at the top, a "higher" work function is illustrated as being farther away from the vacuum level in the downward direction. Thus, the definitions of HOMO and LUMO energy levels follow a different convention than work functions.

[0017] Layers, materials, regions, and devices can be described herein in terms of the color of light they emit. Generally, as used herein, a light-emitting region described as producing light of a particular color can include one or more light-emitting layers arranged together in a stack.

[0018] As used herein, "NIR" layer, "red" layer, "green" layer, "blue" layer, "yellow" layer, material, region, or device refers to a layer, material, region, or device that emits light in the wavelength ranges of approximately 700-1500 nm, 580-700 nm, 500-600 nm, 400-500 nm, or 540-600 nm, respectively, or a layer, material, region, or device that has the highest peak in its emission spectrum in each wavelength range. In some configurations, separate regions, layers, materials, or devices can provide separate "dark blue" and "light blue" emissions. As used herein, a "dark blue" emissive component refers to an emission having a peak emission wavelength that is at least about 4 nm shorter than the peak emission wavelength of the "light blue" emissive component. Typically, the "light blue" emissive component has a peak emission wavelength in the range of about 465-500 nm, and the "dark blue" emissive component has a peak emission wavelength in the range of about 400-470 nm, although these ranges can vary in some configurations.

[0019] In some configurations, a color-changing layer is provided that converts, modifies, or shifts the color of light emitted by another layer to an emission having a different wavelength. Such color-changing layers can be formulated to shift the wavelength of light emitted by another layer by a specified amount, as measured by the difference between the wavelength of the emitted light and the wavelength of the resulting light. Generally, there are two classes of color-changing layers: color filters that modify the spectrum by filtering out undesired wavelengths of light, and color-changing layers that convert higher-energy photons to lower-energy photons. For example, a "red" color filter can be present to filter input light to filter out light having wavelengths outside the range of approximately 580-700 nm. A "color" component refers to a component that, when activated or used, produces or emits light having a particular color, as described above. For example, a "first light-emitting region of a first color" and a "second light-emitting region of a second color different from the first color" refer to two light-emitting regions that, when activated within a device, emit two different colors, as described above.

[0020] As used herein, light-emitting materials, layers, and regions can be distinguished from one another and from other structures based on the light initially produced by the material, layer, or region, as opposed to the light ultimately emitted by the same or a different structure. Typically, the initial generation of light is the result of an energy level change that results in the emission of a photon. For example, an organic light-emitting material may initially produce blue light, which may be converted to red or green light by a color filter, quantum dot, or other structure, such that the complete light-emitting stack or subpixel emits red or green light. In this case, the initial light-emitting material, region, or layer may be referred to as the "blue" component, even if the subpixel is the "red" or "green" component.

[0021] In some instances, it may be preferable to describe the color of components of light-emitting regions, subpixels, color-changing layers, etc., in 1931 CIE coordinates. For example, a yellow light-emitting material may have multiple peak emission wavelengths, one within or near the edge of the "green" region as described above, and another within or near the edge of the "red" region. Thus, as used herein, each color term also corresponds to a shape in the 1931 CIE coordinate color space. A shape in the 1931 CIE color space is constructed by tracing the coordinates between two color points and any additional internal points. For example, the internal shape parameters for red, green, blue, and yellow may be defined as follows: TIFF2026026030000003.tif76170

[0022] The terms "halo," "halogen," and "halide" are used interchangeably and refer to fluorine, chlorine, bromine, and iodine.

[0023] The term "acyl" refers to a substituted carbonyl group (-C(O)-R s ) refers to

[0024] The term "ester" refers to a substituted oxycarbonyl (-OC(O)-R s or -C(O)-OR s ) group.

[0025] The term "ether" means -OR s Refers to the base.

[0026] The terms "sulfanyl" and "thioether" are used interchangeably, and -SR s Refers to the base.

[0027] The term "selenyl" means -SeR s Refers to the base.

[0028] The term "sulfinyl" refers to -S(O)-R s Refers to the base.

[0029] The term "sulfonyl" means -SO2-R s Refers to the base.

[0030] The term "phosphino" refers to a group that contains at least one phosphorus atom bonded to the relevant structure. Common examples of phosphino groups include -P(R s )2 groups or -PO(R s ) groups, but are not limited to these, and each R s may be the same or different.

[0031] The term "silyl" refers to a group that contains at least one silicon atom bonded to the associated structure. Common examples of silyl groups include -Si(R s )3 groups (in the formula, each R s may be the same or different).

[0032] The term "germyl" refers to a group that contains at least one germanium atom bonded to the relevant structure. A common example of a germyl group is -Ge(R s )3 groups (in the formula, each R s may be the same or different).

[0033] The term "boryl" refers to a group that contains at least one boron atom bonded to the relevant structure. Common examples of boryl groups include -B(R s )2 group or its Lewis adduct -B(R s )3 groups (in the formula, R s may be the same or different).

[0034] In each of the above, R s can be hydrogen or a substituent selected from the group consisting of General Substituents defined in this application. sis selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, and combinations thereof. s is selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0035] The term "alkyl" refers to and includes both straight-chain and branched-chain alkyl groups having alkyl carbon atoms attached to the relevant structure. Preferred alkyl groups contain 1 to 15 carbon atoms, preferably 1 to 9 carbon atoms. Preferred alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1,3-dimethylpropyl, 1,1-dimethylpropyl, 2-ethylpropyl, 1,2-dimethylpropyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, n-heptyl, 2-methylhexyl, 3-methylhexyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl, 3,3-dimethylpentyl, 3-ethylpentyl, 2,2,3-trimethylbutyl, and the like. In addition, alkyl groups may be further substituted.

[0036] The term "cycloalkyl" refers to and includes monocyclic, polycyclic, and spiroalkyl groups having ring alkyl carbon atoms attached to the related structure. Preferred cycloalkyl groups contain 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, and the like. In addition, cycloalkyl groups may be further substituted.

[0037] The terms "heteroalkyl" or "heterocycloalkyl" refer to an alkyl or cycloalkyl group, respectively, having at least one carbon atom replaced by a heteroatom. Optionally, the at least one heteroatom is selected from O, S, N, P, B, Si, Ge, and Se, preferably O, S, or N. In addition, the heteroalkyl or heterocycloalkyl group may be further substituted.

[0038] The term "alkenyl" refers to and includes both straight-chain and branched-chain alkene groups. Alkenyl groups are essentially alkyl groups containing at least one carbon-carbon double bond in the alkyl chain, with one carbon atom attached to the related structure from the carbon-carbon double bond. Cycloalkenyl groups are essentially cycloalkyl groups containing 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, the at least one heteroatom is selected from O, S, N, P, B, Si, Ge, and Se, preferably O, S, or N. Preferred alkenyl, cycloalkenyl, or heteroalkenyl groups are those containing 2 to 15 carbon atoms. In addition, the alkenyl, cycloalkenyl, or heteroalkenyl groups may be further substituted.

[0039] The term "alkynyl" refers to and includes both straight-chain and branched-chain alkyne groups. Alkynyl groups are essentially alkyl groups containing at least one carbon-carbon triple bond in the alkyl chain, with one carbon atom from the carbon-carbon triple bond connecting the related structure. Preferred alkynyl groups are those containing 2 to 15 carbon atoms. In addition, the alkynyl groups may be further substituted.

[0040] The terms "aralkyl" or "arylalkyl" are used interchangeably and refer to an alkyl group substituted with an aryl group having an alkyl carbon atom attached to the related structure. In addition, said aralkyl group may be further substituted.

[0041] The term "heterocyclic group" refers to and includes aromatic and non-aromatic cyclic groups containing at least one heteroatom. Optionally, the at least one heteroatom is selected from O, S, Se, N, P, B, Si, Ge, and Se, preferably O, S, N, or B. Heteroaromatic cyclic groups may be used interchangeably with heteroaryl. Preferred heteroaromatic cyclic groups contain 3 to 10 ring atoms, preferably 3 to 7 ring atoms, and include at least one heteroatom, including cyclic amines such as morpholino, piperidino, and pyrrolidino, and cyclic ethers / thioethers such as tetrahydrofuran, tetrahydropyran, and tetrahydrothiophene. In addition, the heterocyclic groups may be further substituted or fused.

[0042] The term "aryl" refers to and includes both monocyclic and polycyclic aromatic hydrocarbyl groups. Polycyclic rings can have two or more rings in which two carbon atoms are shared between two adjacent rings (the rings are "fused"). Preferred aryl groups contain 6 to 30 carbon atoms, with 6 to 24 carbon atoms being preferred, and 6 to 18 carbon atoms being more preferred, with 6 to 12 carbon atoms being more preferred. Aryl groups having 6 carbon atoms, 10 carbon atoms, 12 carbon atoms, 14 carbon atoms, or 18 carbon atoms are particularly preferred. Suitable aryl groups include phenyl, biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, pyrene, chrysene, perylene, and azulene, with phenyl, biphenyl, triphenyl, triphenylene, and naphthalene being preferred. Additionally, the aryl group may be further substituted or fused to, for example, but not limited to, fluorene.

[0043] The term "heteroaryl" refers to and includes both monocyclic aromatic groups and polycyclic aromatic ring systems containing at least one heteroatom. Heteroatoms include, but are not limited to, O, S, Se, N, P, B, Si, Ge, and Se. In many instances, O, S, N, or B are preferred heteroatoms. Heteromonocyclic aromatic systems are preferably monocyclic rings having 5 or 6 ring atoms, and the ring can have 1 to 6 heteroatoms. Heteropolycyclic ring systems can have two or more aromatic rings in which two atoms are common to two adjacent rings (the rings are "fused"), and at least one of the rings is heteroaryl. Heteropolycyclic aromatic ring systems can have 1 to 6 heteroatoms per ring of the polycyclic aromatic ring system. Preferred heteroaryl groups are those containing 3 to 30 carbon atoms, with those containing 3 to 24 carbon atoms being preferred, those containing 3 to 18 carbon atoms being preferred, and those containing 3 to 12 carbon atoms being more preferred. 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, o Xadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, selenophenodipyridine, azaborine, borazine, 5λ 2 ,9λ 2 -diaza-13b-boranaphtho[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 -diaza-13b-boranaphtho[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. In addition, the heteroaryl group may be further substituted or fused.

[0044] Among the aryl and heteroaryl groups listed above, triphenylene, naphthalene, anthracene, dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, pyrazine, pyrimidine, triazine, benzimidazole, 5λ 2 ,9λ 2 -diaza-13b-boranaphtho[2,3,4-de]anthracene, 5λ 2 Of particular interest are the groups -benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, 5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene, as well as their respective aza analogues.

[0045] In many instances, the General Substituents are selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, selenyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

[0046] In some instances, 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, sulfanyl, and combinations thereof.

[0047] In some instances, more preferred common substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, aryl, heteroaryl, nitrile, sulfanyl, and combinations thereof.

[0048] In some instances, even more preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, silyl, aryl, heteroaryl, nitrile, and combinations thereof.

[0049] In still other instances, the most preferred general substituents are selected from the group consisting of deuterium, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0050] One or more substituents (e.g., R, R', R'', R A , R A , R 1 , R, etc.) are not specifically defined, each of the one or more substituents shall be understood to independently represent hydrogen or a substituent selected from the group consisting of the general substituents defined herein. Similarly, each of the one or more substituents may optionally be combined or fused with another substituent to form a ring. It shall also be understood that any substituent that may be selected from the general substituents defined herein may also be selected from a preferred general substituent defined herein, a more preferred general substituent defined herein, an even more preferred general substituent defined herein, or a most preferred general substituent defined herein.

[0051] The terms "substituted" and "substituted" refer to a substituent other than H attached to the relevant position (e.g., carbon or nitrogen). For example, R 1 If represents a single substitution, one R 1 must be other than H (i.e., a substitution). Similarly, R 1 If represents a disubstitution, R 1 must be other than H. Similarly, R 1 When represents zero or no substitution, R 1 can be hydrogens on all available valences of the ring atoms, as in the case of carbon atoms in benzene and nitrogen atoms in pyrrole, or simply represent nothing in the case of ring atoms with fully satisfied valences (e.g., nitrogen atoms in pyridine). The maximum number of substitutions possible in a ring structure depends on the total number of available valences on the ring atoms.

[0052] As used herein, "combinations thereof" refers to one or more members of the applicable list being combined to form known or chemically stable configurations that one skilled in the art can contemplate from the applicable list. For example, alkyl and deuterium can be combined to form a partially or fully deuterated alkyl group; halogen and alkyl can be combined to form a halogenated alkyl substituent; halogen, alkyl, and aryl can be combined to form a halogenated arylalkyl. In one example, the term "substituted" includes combinations of 2 to 4 of the listed groups. In another example, the term "substituted" includes combinations of 2 to 3 groups. In yet another example, the term "substituted" includes combinations of 2 groups. Preferred combinations of substituents are those containing up to 50 atoms that are not hydrogen or deuterium, or those containing up to 40 atoms that are not hydrogen or deuterium, or those containing up to 30 atoms that are not hydrogen or deuterium. In many examples, preferred combinations of substituents include up to 20 atoms that are not hydrogen or deuterium.

[0053] The designation "aza" in the fragments described herein, i.e., aza-dibenzofuran, aza-dibenzothiophene, etc., means that one or more of the C—H groups in each aromatic ring can be replaced by a nitrogen atom; for example, but not by any limitation, azatriphenylene encompasses both dibenzo[f,h]quinoxaline and dibenzo[f,h]quinoline. One skilled in the art can easily imagine other nitrogen analogs of the above-described aza derivatives, and all such analogs are intended to be encompassed by the term described herein.

[0054] The present disclosure includes all permissible isotopically labeled compounds of the present disclosure in which one or more atoms are replaced by an atom having the same atomic number but an atomic mass or mass number different from the atomic mass or mass number normally found in nature.

[0055] Examples of isotopes suitable for inclusion in compounds of the present disclosure include: 2 H and 3 Hydrogen such as H 11 C. 13 C and 14 Carbon, such as C 36 chlorine such as Cl, 18 Fluorine such as F, 123 I, 124 I and 125 Iodine, such as I 13 N and 15 Nitrogen such as N 15 O. 17 O and 18 Oxygen, such as O 32 Phosphorus, such as P, and 35 Examples include sulfur isotopes such as S.

[0056] Certain isotopically labeled compounds of the present disclosure, for example, compounds incorporating radioactive isotopes, are useful in diagnostics and other research. The radioactive isotope tritium, i.e. 3 H, and carbon-14, i.e. 14 C are particularly useful for this purpose in view of their ease of incorporation and ready means of detection.

[0057] Deuterium, i.e. 2 Substitution with heavier isotopes such as H may offer certain advantages through increased stability and may therefore be preferred in some circumstances.

[0058] Isotopically labeled compounds of the present invention can generally be prepared by conventional techniques known to those skilled in the art or by processes analogous to those described in the accompanying examples and procedures, using appropriate isotopically labeled reagents in place of conventionally used non-labeled reagents.

[0059] For example, deuterated compounds can be easily prepared using methods known in the art. For example, U.S. Patent No. 8,557,400, Patent Publication No. WO2006 / 095951, and U.S. Patent Application Publication No. US2011 / 0037057 (the entire contents of which are incorporated by reference) describe the preparation of deuterated organometallic complexes. See also Tetrahedron 2015, 71, 1425-30 (Ming Yan et al.) and Angew. Chem. Int. Ed. (Reviews) 2007, 46, 7744-65 (Atzrodt et al.) (the entire contents of which are incorporated by reference). These describe efficient routes for deuterium deuteration of methylene hydrogens in benzylamines and for replacing aromatic ring hydrogens with deuterium, respectively.

[0060] As used herein, any specifically recited substituent, such as, but not limited to, methyl, phenyl, pyridyl, etc., includes undeuterated, partially deuterated, and fully deuterated versions thereof. Similarly, substituent classes, such as, but not limited to, alkyl, aryl, cycloalkyl, heteroaryl, etc., also include undeuterated, partially deuterated, and fully deuterated versions thereof. Unless otherwise specified, atoms in a chemical structure that do not have valences fully filled with H or D should be considered to include their undeuterated, partially deuterated, and fully deuterated versions. For example, the chemical structure [ka] is meant to include C6H6, C6D6, C6H3D3, and any other partially deuterated variants thereof. Some common basic groups that are partially or fully deuterated include, but are not limited to, CD3, CD2C(CH3)3, C(CD3)3, and C6D5. Similarly, when a partially or fully defined atomic structure indicates that a particular position can be or is deuterium, the same atomic structure is also envisioned with one, two, or up to all deuterium atoms replaced with hydrogen.

[0061] When a molecular fragment is described as being a substituent or as being attached to another moiety, it is understood that the name can be described as either the fragment (e.g., phenyl, phenylene, naphthyl, dibenzofuryl) or the entire molecule (e.g., benzene, naphthalene, dibenzofuran). As used herein, different designations of the substituent or attached fragment are considered equivalent.

[0062] In some instances, pairs of substituents in a molecule can be bonded or fused to form a ring. Preferred rings are 5- to 9-membered carbocyclic or heterocyclic rings, including both saturated and unsaturated rings. In yet other instances, adjacent pairs of substituents can be bonded or fused to form a ring. As used herein, "adjacent" means that the two related substituents can be adjacent to each other on the same ring, or can be adjacent to each other on two rings that have the two nearest available substitutable positions, such as the 2- and 2'-positions in biphenyl or the 1- and 8-positions in naphthalene.

[0063] B. Compounds of the Present Disclosure In one aspect, the present disclosure provides a compound comprising a first ligand L A wherein the first ligand L A has the structure of Formula I: [ka] (In the formula, Moieties A and D are each independently a monocyclic ring or a polycyclic fused ring system, and each ring of the monocyclic ring or polycyclic fused ring system is independently a 5- to 10-membered carbocyclic or heterocyclic ring; The moiety C is a 5- or 6-membered carbocyclic or heterocyclic ring; Z 1 , Z 2 and X 1 ~X 4 each is independently C or N; Part A is X 1 ~X 4 and binds to one of the X 1 ~X 4 One of them is C; Y is selected from the group consisting of BR, BRR', NR, PR, P(O)R, O, S, Se, C=O, C=S, C=Se, C=NR', C=CRR', S=O, SO2, CR, CRR', SiRR', and GeRR'; K is 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 ) selected from the group consisting of; R A , R B , R C , and R D each independently represents one to the maximum number of substitutions or no substitutions; Each R, R', R α , R β , R A , R B , R C , and R D is independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boryl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, selenyl, and combinations thereof; At least one R C or R D is a substituent R containing a carbocyclic or heterocyclic group * ) L A is coordinated to the metal M; M is selected from the group consisting of Ir, Rh, Re, Ru, Os, Pt, Pd, Ag, Au, and Cu; M may be coordinated to other ligands; L A may, in combination with other ligands, comprise a tridentate, tetradentate, pentadentate, or hexadentate ligand; and Any two substituents may be joined or fused to form a ring, to provide a compound.

[0064] Z 1 -Z 2Although the bonds between are shown as single bonds, it should be understood that they may be any other bond necessary to make the applicable cyclic portion of the moiety. This also applies to any other generalized ring or moiety disclosed herein.

[0065] In some embodiments, the compound consists essentially of Formula I. In some embodiments, the compound has the structure of Formula I.

[0066] In some embodiments, the moiety C is a 6-membered ring and R C or R D R * If R * is not an unsubstituted phenyl group or a phenyl group substituted with an electron-withdrawing group. In some embodiments, the moiety C is a 6-membered ring and R C or R D is R * and the above R * is not an unsubstituted phenyl group or a phenyl group substituted with an electron-withdrawing group.

[0067] In some embodiments, moieties C and D together form a naphthalene ring, and R C R * If R * is not unsubstituted carbazole, 2,7-di-tert-butyl-carbazole, or 3,5-di-tert-butyl-carbazole. In some embodiments, moieties C and D together form a naphthalene ring, and R C is R * and the above R * is not unsubstituted carbazole, 2,7-di-tert-butyl-carbazole, or 3,5-di-tert-butyl-carbazole.

[0068] In some embodiments, R D R * If R * The following list RD: [ka] In some embodiments, R D is R * and the above R * is not selected from the list RD defined herein.

[0069] In some embodiments, each R, R′, R α , R β , R A , R B , R C , and R D are independently hydrogen or a substituent selected from the group consisting of preferred general substituents defined herein. In some embodiments, each R, R', R α , R β , R A , R B , R C , and R D are independently hydrogen or a substituent selected from the group consisting of the more preferred general substituents defined herein. In some embodiments, each R, R', R α , R β , R A , R B , R C , and R D are independently hydrogen or a substituent selected from the group consisting of the more preferred general substituents defined herein. In some embodiments, each R, R', R α , R β , R A , R B , R C , and R D is independently hydrogen or a substituent selected from the group consisting of the most preferred general substituents defined herein.

[0070] In some embodiments, at least one R A , R B , R C , or R D is selected from the group consisting of general substituents defined herein. In some embodiments, at least one R Ais selected from the group consisting of general substituents defined herein. In some embodiments, at least one R B is selected from the group consisting of general substituents defined herein. In some embodiments, at least one R C is selected from the group consisting of general substituents defined herein. In some embodiments, at least one R D is selected from the group consisting of general substituents defined herein. In some embodiments, at least one R A , R B , R C , or R D is selected from the group of preferred general substituents defined herein.

[0071] In some embodiments of Formula I, at least one of R, R′, R α , R β , R A , R B , R C , or R D is partially or fully deuterated. In some embodiments, at least one R A is partially or fully deuterated. In some embodiments, at least one R B is partially or fully deuterated. In some embodiments, at least one R C is partially or fully deuterated. In some embodiments, R D is partially or fully deuterated. In some embodiments, at least one of R or R' is partially or fully deuterated. In some embodiments, R α or R β At least one of is partially or fully deuterated.

[0072] In some embodiments, R, R′, R α , R β , R A , R B , R C , and R Dis independently hydrogen or a substituent selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, and combinations thereof.

[0073] In some embodiments, each of moieties A and D is independently selected from the following list of cyclic moieties: benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole, triazole, cyclopentadiene, selenophene, naphthalene, quinoline, isoquinoline, quinazoline, benzofuran, aza-benzofuran, phenanthro[3,2-b]benzofuran, benzoxazole, aza-benzoxazole, benzothiophene, aza-benzothiophene, benzothiazole, aza-benzothiazole, benzo In some embodiments, the azavariant is selected from the group consisting of azaselenophene, aza-benzoselenophene, indene, aza-indene, indole, aza-indole, benzimidazole, aza-benzimidazole, benzobenzimidazole, aza-benzobenzimidazole, carbazole, aza-carbazole, naphtho-imidazole, dibenzofuran, aza-dibenzofuran, dibenzothiophene, aza-dibenzothiophene, quinoxaline, phthalazine, phenanthrene, aza-phenanthrene, anthracene, aza-anthracene, phenanthridine, fluorene, and aza-fluorene. In some embodiments, the azavariant includes at least one N on the fused benzene ring.

[0074] In some embodiments, moiety A is a monocyclic ring.

[0075] In some embodiments, the moiety A is selected from the group consisting of benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole, and triazole.

[0076] In some embodiments, moiety A is benzene, pyrimidine, or pyridine. In some embodiments, moiety A is benzene. In some embodiments, moiety A is pyrimidine. In some embodiments, moiety A is pyridine.

[0077] In some embodiments, moiety A is a polycyclic fused ring system.

[0078] In some embodiments, the moiety A 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, benzobenzimidazole, aza-benzobenzimidazole, carbazole, aza-carbazole, naphtho-imidazole, dibenzofuran, aza-dibenzofuran, dibenzothiophene, aza-dibenzothiophene, quinoxaline, phthalazine, phenanthrene, aza-phenanthrene, anthracene, aza-anthracene, phenanthridine, fluorene, and aza-fluorene.

[0079] In some embodiments, moiety A is naphthalene or isoquinoline. In some embodiments, moiety A is naphthalene. In some embodiments, moiety A is isoquinoline.

[0080] In some embodiments, moiety D is a monocyclic ring.

[0081] In some embodiments, moiety D is selected from the group consisting of benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole, and triazole.

[0082] In some embodiments, moiety D is benzene, pyridine, oxazole, furan, thiazole, or imidazole. In some embodiments, moiety D is benzene. In some embodiments, moiety D is pyridine. In some embodiments, moiety D is oxazole. In some embodiments, moiety D is furan. In some embodiments, moiety D is thiazole. In some embodiments, moiety D is imidazole.

[0083] In some embodiments, moiety D is a polycyclic fused ring system.

[0084] In some embodiments, moiety D contains exactly two fused rings.

[0085] In some embodiments, moiety D comprises at least three fused rings.

[0086] In some embodiments, moiety D comprises at least one five-membered ring and at least one six-membered ring.

[0087] In some embodiments, moiety D comprises at least two six-membered rings.

[0088] In some embodiments, the moiety D is selected from the group consisting of naphthalene, quinoline, isoquinoline, quinazoline, benzofuran, aza-benzofuran, phenanthro[3,2-b]benzofuran, benzoxazole, aza-benzoxazole, benzothiophene, aza-benzothiophene, benzothiazole, aza-benzothiazole, benzoselenophene, aza-benzoselenophene, indene, aza-indene, indole, aza-indole, benzimidazole, aza-benzimidazole, carbazole, aza-carbazole, naphtho-imidazole, dibenzofuran, aza-dibenzofuran, dibenzothiophene, aza-dibenzothiophene, quinoxaline, phthalazine, phenanthrene, aza-phenanthrene, anthracene, aza-anthracene, phenanthridine, fluorene, and aza-fluorene. In some embodiments, moiety D comprises a 5-membered ring fused to moiety C.

[0089] In some embodiments, moiety D comprises benzofuran, benzothiophene, indole, or benzoselenophene. In some embodiments, moiety D is benzofuran. In some embodiments, moiety D is benzothiophene. In some embodiments, moiety D is indole. In some embodiments, moiety D is benzoselenophene.

[0090] In some embodiments, moiety D is naphthalene or quinoline. In some embodiments, moiety D is naphthalene. In some embodiments, moiety D is quinoline.

[0091] In some embodiments, each of moieties A and D is independently a monocyclic ring or a polycyclic fused ring system, and each ring of the monocyclic ring or polycyclic fused ring system is independently a 5- or 6-membered carbocyclic or heterocyclic ring.

[0092] In some embodiments, each of moieties A and D is independently a monocyclic ring or a polycyclic fused ring system, and each ring of the monocyclic ring or polycyclic fused ring system is independently a 5- or 6-membered aryl or heteroaryl ring.

[0093] In some embodiments, at least one of moieties A and D can independently be a polycyclic fused ring structure. In some embodiments, at least one of moieties A and D can independently be a polycyclic fused ring structure comprising at least two fused rings. In some embodiments, the polycyclic fused ring structure has one six-membered ring and one five-membered ring. In some such embodiments, either the five-membered ring or the six-membered ring can coordinate to a metal. In some embodiments, the polycyclic fused ring structure has two six-membered rings. In some embodiments, at least one of moieties A and D can independently be selected from the group consisting of benzofuran, benzothiophene, benzoselenophene, naphthalene, and azavariants thereof.

[0094] In some embodiments, at least one of moieties A and D can independently be a polycyclic fused ring structure comprising at least three fused rings. In some embodiments, the polycyclic fused ring structure has two six-membered rings and one five-membered ring. In some such embodiments, a five-membered ring is fused to a ring coordinated to the metal M, and a second six-membered ring is fused to the five-membered ring. In some embodiments, at least one of moieties A and D can independently be selected from the group consisting of dibenzofuran, dibenzothiophene, dibenzoselenophene, and azavariants thereof. In some such embodiments, at least one of moieties A and D can independently be further substituted at the ortho- or meta-position of the O, S, or Se atom with a substituent selected from the group consisting of deuterium, fluorine, nitrile, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof. In some such embodiments, the azavariant contains exactly one N atom at the 6-position (ortho to the O, S, or Se) and has a substituent at the 7-position (meta to the O, S, or Se).

[0095] In some embodiments, at least one of moieties A and D can independently be a polycyclic fused ring structure comprising at least four fused rings. In some embodiments, the polycyclic fused ring structure comprises three six-membered rings and one five-membered ring. In some such embodiments, a five-membered ring is fused to a ring coordinated to metal M, a second six-membered ring is fused to the five-membered ring, and a third six-membered ring is fused to the second six-membered ring. In some such embodiments, the third six-membered ring is further substituted with a substituent selected from the group consisting of deuterium, fluorine, nitrile, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0096] In some embodiments, at least one of moieties A and D can independently be a polycyclic fused ring structure comprising at least five fused rings. In some embodiments, the polycyclic fused ring structure comprises four six-membered rings and one five-membered ring, or three six-membered rings and two five-membered rings. In some embodiments comprising two five-membered rings, the five-membered rings are fused together. In some embodiments comprising two five-membered rings, the five-membered rings are separated by at least one six-membered ring. In some embodiments having one five-membered ring, a five-membered ring is fused to the ring coordinated to the metal M, a second six-membered ring is fused to the five-membered ring, a third six-membered ring is fused to the second six-membered ring, and a fourth six-membered ring is fused to the third six-membered ring.

[0097] In some embodiments, at least one of moieties A and D may independently be an aza version of the polycyclic fused ring described above. In some such embodiments, at least one of moieties A and D may independently contain exactly one aza N atom. In some such embodiments, at least one of moieties A and D may independently contain exactly two aza N atoms, which may be in one ring or in two different rings. In some such embodiments, the ring containing the aza N atom is separated from the metal M atom by at least two other rings. In some such embodiments, the ring containing the aza N atom is separated from the metal M atom by at least three other rings. In some such embodiments, each of the ortho positions of the aza N atom is substituted. In some embodiments, moiety C is a 5-membered ring. In some embodiments, moiety C is a 5-membered aromatic ring. In some embodiments, moiety C is a 5-membered non-aromatic ring.

[0098] In some embodiments, moiety C is a 6-membered ring. In some embodiments, moiety C is a 6-membered aromatic ring. In some embodiments, moiety C is a 6-membered non-aromatic ring.

[0099] In some embodiments, moiety C is cyclopentadiene, furan, thiophene, pyrrole, or selenophene. In some embodiments, moiety C is cyclopentadiene. In some embodiments, moiety C is furan. In some embodiments, moiety C is thiophene. In some embodiments, moiety C is pyrrole. In some embodiments, moiety C is selenophene.

[0100] In some embodiments, moiety C is benzene, pyridine, pyridazine, or pyrazine. In some embodiments, moiety C is benzene. In some embodiments, moiety C is pyridine. In some embodiments, moiety C is pyridazine. In some embodiments, moiety C is pyrazine.

[0101] In some embodiments, the moiety C is a 5- or 6-membered aryl or heteroaryl ring.

[0102] In some embodiments, Z 1 is N and Z 2 is C. In some embodiments, Z 1 is C and Z 2 is N.

[0103] In some embodiments, Z 1 and Z 2 Each of is N.

[0104] In some embodiments, Z 1 and Z 2 Each of is C.

[0105] In some embodiments, X 1 ~X 4 Each of is C.

[0106] In some embodiments, X 1 ~X 4 At least one of X is N. In some embodiments, 1 ~X 4 Exactly one of is N.

[0107] In some embodiments, X 1 is N. In some embodiments, X 2 is N. In some embodiments, X 3 is N. In some embodiments, X 4 is N.

[0108] In some embodiments, Y is selected from the group consisting of O, S, and Se.

[0109] In some embodiments, Y is O.

[0110] In some embodiments, Y is selected from the group consisting of BR, NR, and PR.

[0111] In some embodiments, Y is selected from the group consisting of BRR', CRR', SiRR', GeRR', and PRR'.

[0112] In some embodiments, Y is selected from the group consisting of P(O)R, C=O, C=S, C=Se, C=NR, C=CRR', S=O, and SO2.

[0113] In some embodiments, Y is CR.

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

[0115] In some embodiments, K is O or S.

[0116] In some embodiments, K is O.

[0117] In some embodiments, K is N(R α ), P(R α ), or B(R α )

[0118] In some embodiments, K is C(R α )(R β ) or Si(R α )(R β )

[0119] 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 greater than or equal to 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, or 1.1.

[0120] In some embodiments, the first ligand L Acontains 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 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 group-containing alkyl, cyano group-containing aryl, cyano group-containing heteroaryl, isocyanate, [ka] (In the formula, each R k1 represents one to the maximum number of substitutions allowed, or no substitutions; Y G BR e , N.R. e , PR e , O, S, S e , C=O, S=O, SO2, CR e R f , SiR e R f , and G e R eR f selected from the group consisting of: R k1 , R k2 , R k3 , R e , and R f each independently is hydrogen or a substituent selected from the group consisting of the general substituents defined herein).

[0121] In some embodiments, the first ligand L A comprises an electron withdrawing group selected from the group consisting of the structures in the EWG2 list below: [ka] [ka]

[0122] In some embodiments, the first ligand L A comprises an electron withdrawing group selected from the group consisting of the structures in the EWG3 list below: [ka]

[0123] In some embodiments, the ligand L A comprises an electron withdrawing group selected from the group consisting of the structures in the EWG4 list below: [ka]

[0124] In some embodiments, the first ligand L A comprises a π-electron deficient electron withdrawing group selected from the group consisting of structures from 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(Rk2 )3, BR k2 R k3 , 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 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 group-containing aryl, cyano group-containing heteroaryl, isocyanate, [ka] where the variables are the same as defined above.

[0125] In some embodiments, at least one R A is not hydrogen. In some embodiments, at least two R A is not hydrogen.

[0126] In some embodiments, at least one R A contains at least one carbon atom. In some embodiments, at least one R A contains at least two carbon atoms. In some embodiments, at least one R A contains at least 3 carbon atoms. In some embodiments, at least one R A contains at least 4 carbon atoms. In some embodiments, at least two R A independently contain at least one carbon atom.

[0127] In some embodiments, at least one RA In some embodiments, at least two R A In some embodiments, at least two R A is alkyl.

[0128] In some embodiments, two R A are linked or fused to form a cyclic moiety A2. In some embodiments, the cyclic moiety A2 is selected from the group consisting of the list of cyclic moieties defined herein.

[0129] In some embodiments, each R B is H.

[0130] In some embodiments, at least one R B is not hydrogen.

[0131] In some embodiments, at least one R B contains at least one carbon atom. In some embodiments, at least one R B contains at least two carbon atoms. In some embodiments, at least one R B contains at least 3 carbon atoms. In some embodiments, at least one R B contains at least four carbon atoms.

[0132] In some embodiments, at least one R B includes substituents selected from the group consisting of alkyl, cycloalkyl, silyl, germyl, aryl, heteroaryl, and combinations thereof.

[0133] In some embodiments, two R Bare linked or fused to form cyclic moiety B2. In some embodiments, cyclic moiety B2 is selected from the group consisting of the list of cyclic moieties defined herein.

[0134] In some embodiments, at least one R C is not hydrogen.

[0135] In some embodiments, at least one R C contains at least one carbon atom. In some embodiments, at least one R C contains at least two carbon atoms. In some embodiments, at least one R C contains at least 3 carbon atoms. In some embodiments, at least one R C contains at least four carbon atoms.

[0136] In some embodiments, at least one R C includes substituents selected from the group consisting of alkyl, cycloalkyl, silyl, germyl, aryl, heteroaryl, and combinations thereof.

[0137] In some embodiments, at least one R C is the substituent R * In some embodiments, at least one R C is the substituent R * and the substituent R * includes substituted aryl or heteroaryl.

[0138] In some embodiments, at least one R C is the substituent R * and the substituent R * is a structure of formula II [ka] (In the formula, Ring F is a 5- to 10-membered carbocyclic or heterocyclic ring; R Frepresents mono- to tri-substituted or unsubstituted; Each R 1’ , R 2’ , and R F is independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, selenyl, and combinations thereof; and R 1’ or R 2’ at least one of which is not hydrogen or deuterium).

[0139] In some embodiments, ring F is a 5- or 6-membered carbocyclic or heterocyclic ring. In some embodiments, ring F is a 5- or 6-membered aryl or heteroaryl ring.

[0140] In some embodiments, at least one R F is or includes an electron withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R F is or includes an electron withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R F is or includes an electron withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R F is or includes 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.

[0141] In some embodiments, R 1’ MoR 2’ is neither hydrogen nor deuterium.

[0142] In some embodiments, R 1’ and R 2’ is independently selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, silyl, germyl, and combinations thereof.

[0143] In some embodiments, R 1’ and R 2’ are the same. In some embodiments, R 1’ and R 2’ is different.

[0144] In some embodiments, R 1’ and R 2’ Each of R contains at least one carbon atom. 1’ and R 2’ Each of R contains at least two carbon atoms. 1’ and R 2’ Each of R contains at least 3 carbon atoms. 1’ and R 2’ Each of R contains at least 4 carbon atoms. 1’ and R 2’ Each of contains at least 5 carbon atoms.

[0145] In some embodiments, at least one R F is not hydrogen or deuterium.

[0146] In some embodiments, at least one R F is selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, silyl, germyl, and combinations thereof.

[0147] In some embodiments, ring F is selected from the group consisting of benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, imidazole-derived carbenes, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole, and triazole.

[0148] In some embodiments, at least one R C is the substituent R * and the substituent R * is a structure of formula IIA [ka] (In the formula, X 1a , X 2a , and X 3a each of which is independently C or N.

[0149] In some embodiments, X 2a R bound to F is selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, silyl, germyl, and combinations thereof. 2a R bound to F is alkyl. In some embodiments, X 2a R bound to F is aryl or heteroaryl. In some embodiments, X 2a R bound to F is silyl. In some embodiments, X 2a R bound to F is germyl.

[0150] In some embodiments, X 1a , X 2a , and X 3a Each of X is C. In some embodiments, 1a , X 2a , and X 3a At least one of X is N. In some embodiments, 1a , X 2a , and X 3a Exactly one of is N.

[0151] In some embodiments, R F is an aryl group. In some embodiments, R F is benzene.

[0152] In some embodiments, the substituent R * is a monocyclic ring or a polycyclic fused ring system, and each ring of the monocyclic ring or polycyclic fused ring system is independently a 5- to 10-membered carbocyclic or heterocyclic ring.

[0153] In some embodiments, the substituent R * is a cyclic moiety of the following list 2: benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole, triazole, cyclopentadiene, selenophene, selenazole, tellurazole, naphthalene, anthracene, phenanthrene, 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, benzosyl and a cyclic moiety selected from the group consisting of benzosilole, benzotelurophene, benzogermole, benzotelurazole, benzoxazole, benzothiazole, benzoselenazole, carbazole, aza-carbazole, naphtha-imidazole, dibenzofuran, aza-dibenzofuran, dibenzothiophene, aza-dibenzothiophene, quinoxaline, phthalazine, phenanthrene, aza-phenanthrene, anthracene, aza-anthracene, phenanthridine, fluorene, aza-fluorene, dibenzoselenophene, dibenzotellurophene, dibenzosilole, and dibenzogermole.

[0154] In some embodiments, at least one R C is the substituent R * and the substituent R * is a monocyclic ring.

[0155] In some embodiments, at least one R C is the substituent R * and the substituent R * is a substituted phenyl, wherein the substituted phenyl does not contain an electron-withdrawing group.

[0156] In some embodiments, at least one R C is the substituent R * and the substituent R * is a substituted or unsubstituted biphenyl or a substituted or unsubstituted terphenyl.

[0157] In some embodiments, at least one R C is the substituent R * and the substituent R * is selected from the group consisting of substituted or unsubstituted oxazole, substituted or unsubstituted thiazole, substituted or unsubstituted selenazole, substituted or unsubstituted tellurazole, and substituted or unsubstituted imidazole.

[0158] In some embodiments, at least one R C is the substituent R * and the substituent R * is selected from the group consisting of substituted or unsubstituted furan, substituted or unsubstituted thiophene, substituted or unsubstituted selenophene, substituted or unsubstituted tellurophene, and substituted or unsubstituted pyrrole.

[0159] In some embodiments, at least one R C is the substituent R * and the substituent R * is a polycyclic ring system.

[0160] In some embodiments, at least one R C is the substituent R * and the substituent R * contains at least two substituents that are linked or fused to form ring C' of the polycyclic ring system.

[0161] In some embodiments, ring C' is a saturated ring. In some embodiments, ring C' is a 5-membered saturated ring. In some embodiments, ring C' is a 6-membered saturated ring.

[0162] In some embodiments, at least one R C is the substituent R * and the substituent R * further comprises at least two substituents that are linked or fused to form ring C' of the polycyclic ring system.

[0163] In some embodiments, ring C" is a saturated ring. In some embodiments, ring C" is a saturated ring. In some embodiments, ring C" is a 5-membered saturated ring. In some embodiments, ring C" is a 6-membered saturated ring.

[0164] In some embodiments, at least one R C is the substituent R * and the substituent R * is a fused aryl group.

[0165] In some embodiments, at least one R C is the substituent R * and the substituent R * is selected from the group consisting of substituted or unsubstituted naphthalene, substituted or unsubstituted anthracene, and substituted or unsubstituted phenanthrene. In some embodiments, the substituent R * is a substituted or unsubstituted naphthalene. In some embodiments, the substituent R * At least one R C is a substituted or unsubstituted anthracene. In some embodiments, the substituent R *At least one R C is a substituted or unsubstituted phenanthrene.

[0166] In some embodiments, at least one R C is the substituent R * and the substituent R * is a fused heteroaryl group.

[0167] In some embodiments, at least one R C is the substituent R * and the substituent R * is selected from the group consisting of substituted or unsubstituted dibenzofuran, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted carbazole, substituted or unsubstituted dibenzoselenophene, substituted or unsubstituted dibenzotellurophene, substituted or unsubstituted fluorene, substituted or unsubstituted dibenzosilole, and substituted or unsubstituted dibenzogermole.

[0168] In some embodiments, at least one R C is the substituent R * and the substituent R * is a substituted or unsubstituted dibenzofuran or a substituted or unsubstituted carbazole. In some embodiments, the substituent R * At least one R C is a substituted or unsubstituted dibenzofuran. In some embodiments, the substituent R * At least one R C is a substituted or unsubstituted carbazole.

[0169] In some embodiments, at least one R C is the substituent R * and the substituent R *is selected from the group consisting of substituted or unsubstituted benzofuran, substituted or unsubstituted benzothiophene, substituted or unsubstituted benzoselenophene, substituted or unsubstituted benzotellurophene, substituted or unsubstituted indene, substituted or unsubstituted benzosilole, substituted or unsubstituted benzogermole, and substituted or unsubstituted indole.

[0170] In some embodiments, at least one R C is the substituent R * and the substituent R * is selected from the group consisting of substituted or unsubstituted benzoxazole, substituted or unsubstituted benzothiazole, substituted or unsubstituted benzoselenazole, substituted or unsubstituted benzotellurazole, and substituted or unsubstituted benzimidazole.

[0171] In some embodiments, at least one R C is the substituent R * and the substituent R * is deuterated. In some embodiments, at least one R C is the substituent R * and the substituent R * is not deuterated.

[0172] In some embodiments, two R C are bonded or fused to form a ring.

[0173] In some embodiments, at least one R D is not hydrogen.

[0174] In some embodiments, at least one R D contains at least one carbon atom. In some embodiments, at least one R D contains at least two carbon atoms. In some embodiments, at least one R D contains at least 3 carbon atoms. In some embodiments, at least one R Dcontains at least four carbon atoms.

[0175] In some embodiments, at least one R D includes substituents selected from the group consisting of alkyl, cycloalkyl, silyl, germyl, aryl, heteroaryl, and combinations thereof.

[0176] In some embodiments, at least one R D is the substituent R * is.

[0177] In some embodiments, at least one R D is the substituent R * and the substituent R * is a substituted aryl or heteroaryl.

[0178] In some embodiments, at least one R D is the substituent R * and the substituent R * is a substituted aryl or heteroaryl.

[0179] In some embodiments, at least one R D is the substituent R * and the substituent R * is a structure of formula II [ka] (In the formula, Ring F is a 5- to 10-membered carbocyclic or heterocyclic ring; R F represents mono- to tri-substituted or unsubstituted; Each R 1’ , R 2’ , and R Fis independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, selenyl, and combinations thereof; and R 1’ or R 2’ at least one of which is not hydrogen or deuterium).

[0180] In some embodiments, ring F is a 5- or 6-membered carbocyclic or heterocyclic ring. In some embodiments, ring F is a 5- or 6-membered aryl or heteroaryl ring.

[0181] In some embodiments, at least one R F is or includes an electron withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R F is or includes an electron withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R F is or includes an electron withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R F is or includes 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.

[0182] In some embodiments, R 1’ MoR 2’ is neither hydrogen nor deuterium.

[0183] In some embodiments, R 1’ and R 2’is independently selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, silyl, germyl, and combinations thereof.

[0184] In some embodiments, R 1’ and R 2’ are the same. In some embodiments, R 1’ and R 2’ is different.

[0185] In some embodiments, R 1’ and R 2’ Each of R contains at least one carbon atom. 1’ and R 2’ Each of R contains at least two carbon atoms. 1’ and R 2’ Each of R contains at least 3 carbon atoms. 1’ and R 2’ Each of R contains at least 4 carbon atoms. 1’ and R 2’ Each of contains at least 5 carbon atoms.

[0186] In some embodiments, at least one R F is not hydrogen or deuterium.

[0187] In some embodiments, at least one R F is selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, silyl, germyl, and combinations thereof.

[0188] In some embodiments, ring F is selected from the group consisting of benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, imidazole-derived carbenes, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole, and triazole.

[0189] In some embodiments, at least one RD is the substituent R * and the substituent R * is a structure of formula IIA [ka] (In the formula, X 1a , X 2a , and X 3a each of which is independently C or N.

[0190] In some embodiments, X 2a R bound to F is selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, silyl, germyl, and combinations thereof. 2a R bound to F is alkyl. In some embodiments, X 2a R bound to F is aryl or heteroaryl. In some embodiments, X 2a R bound to F is silyl. In some embodiments, X 2a R bound to F is germyl.

[0191] In some embodiments, X 1a , X 2a , and X 3a Each of X is C. In some embodiments, 1a , X 2a , and X 3a At least one of X is N. In some embodiments, 1a , X 2a , and X 3a Exactly one of is N.

[0192] In some embodiments, R F is an aryl group. In some embodiments, R F is benzene.

[0193] In some embodiments, at least one R Dis the substituent R * and the substituent R * is a monocyclic ring or a polycyclic fused ring system, and each ring of the monocyclic ring or polycyclic fused ring system is independently a 5- to 10-membered carbocyclic or heterocyclic ring.

[0194] In some embodiments, at least one R D is the substituent R * and the substituent R * comprises a cyclic moiety selected from the group consisting of the following cyclic moieties List 2 as defined herein.

[0195] In some embodiments, at least one R D is the substituent R * and the substituent R * is a monocyclic ring.

[0196] In some embodiments, at least one R D is the substituent R * and the substituent R * is a substituted phenyl.

[0197] In some embodiments, at least one R D is the substituent R * and the substituent R * is a substituted or unsubstituted biphenyl or a substituted or unsubstituted terphenyl.

[0198] In some embodiments, at least one R D is the substituent R * and the substituent R * is selected from the group consisting of substituted or unsubstituted oxazole, substituted or unsubstituted thiazole, substituted or unsubstituted selenazole, substituted or unsubstituted tellurazole, and substituted or unsubstituted imidazole.

[0199] In some embodiments, at least one R D is the substituent R * and the substituent R *is selected from the group consisting of substituted or unsubstituted furan, substituted or unsubstituted thiophene, substituted or unsubstituted selenophene, substituted or unsubstituted tellurophene, and substituted or unsubstituted pyrrole.

[0200] In some embodiments, at least one R D is the substituent R * and the substituent R * is a polycyclic ring system.

[0201] In some embodiments, at least one R D is the substituent R * and the substituent R * contains at least two substituents that are linked or fused to form ring C' of the polycyclic ring system.

[0202] In some embodiments, ring C' is a saturated ring. In some embodiments, ring C' is a 5-membered saturated ring. In some embodiments, ring C' is a 6-membered saturated ring.

[0203] In some embodiments, at least one R D is the substituent R * and the substituent R * further comprises at least two substituents that are linked or fused to form ring C'' of the polycyclic ring system.

[0204] In some embodiments, ring C" is a saturated ring. In some embodiments, ring C" is a saturated ring. In some embodiments, ring C" is a 5-membered saturated ring. In some embodiments, ring C" is a 6-membered saturated ring.

[0205] In some embodiments, at least one R D is the substituent R * and the substituent R * is a fused aryl group.

[0206] In some embodiments, at least one R D is the substituent R *and the substituent R * is selected from the group consisting of substituted or unsubstituted naphthalene, substituted or unsubstituted anthracene, and substituted or unsubstituted phenanthrene. In some embodiments, the substituent R * At least one R D is a substituted or unsubstituted naphthalene. In some embodiments, the substituent R * At least one R D is a substituted or unsubstituted anthracene. In some embodiments, the substituent R * At least one R D is a substituted or unsubstituted phenanthrene.

[0207] In some embodiments, at least one R D is the substituent R * and the substituent R * is a fused heteroaryl group.

[0208] In some embodiments, at least one R D is the substituent R * and the substituent R * is selected from the group consisting of substituted or unsubstituted dibenzofuran, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted carbazole, substituted or unsubstituted dibenzoselenophene, substituted or unsubstituted dibenzotellurophene, substituted or unsubstituted fluorene, substituted or unsubstituted dibenzosilole, and substituted or unsubstituted dibenzogermole. In some embodiments, the substituent R * At least one R D is a substituted or unsubstituted carbazole.

[0209] In some embodiments, at least one R D is the substituent R * and the substituent R * is a substituted or unsubstituted dibenzofuran or a substituted or unsubstituted carbazole. In some embodiments, the substituent R *At least one R D is a substituted or unsubstituted dibenzofuran. In some embodiments, the substituent R * At least one R D is a substituted or unsubstituted carbazole.

[0210] In some embodiments, at least one R D is the substituent R * and the substituent R * is selected from the group consisting of substituted or unsubstituted benzofuran, substituted or unsubstituted benzothiophene, substituted or unsubstituted benzoselenophene, substituted or unsubstituted benzotellurophene, substituted or unsubstituted indene, substituted or unsubstituted benzosilole, substituted or unsubstituted benzogermole, and substituted or unsubstituted indole.

[0211] In some embodiments, at least one R D is the substituent R * and the substituent R * is selected from the group consisting of substituted or unsubstituted benzoxazole, substituted or unsubstituted benzothiazole, substituted or unsubstituted benzoselenazole, substituted or unsubstituted benzotellurazole, and substituted or unsubstituted benzimidazole.

[0212] In some embodiments, at least one R D is not deuterated.

[0213] In some embodiments, R D is the substituent R * and R * is not a partially or fully deuterated phenyl, a partially or fully deuterated biphenyl, a para-substituted fully deuterated phenyl, a fully deuterated thiophene, a neopentyl-substituted fully deuterated thiophene, or a fully deuterated 2-methylpyridine.

[0214] In some embodiments, at least two R D are bonded or fused to form a ring.

[0215] In some embodiments, at least one R α or R β is not hydrogen.

[0216] In some embodiments, at least one R α or R β contains at least one carbon atom. In some embodiments, at least one R α or R β contains at least two carbon atoms. In some embodiments, at least one R α or R β contains at least 3 carbon atoms. In some embodiments, at least one R α or R β contains at least four carbon atoms.

[0217] In some embodiments, at least one R α or R β includes substituents selected from the group consisting of alkyl, cycloalkyl, silyl, germyl, aryl, heteroaryl, and combinations thereof.

[0218] In some embodiments, R α and R β are bonded or fused to form a ring.

[0219] In some embodiments, at least one R or R' is not hydrogen.

[0220] In some embodiments, at least one R or R' comprises at least 1 carbon atom. In some embodiments, at least one R or R' comprises at least 2 carbon atoms. In some embodiments, at least one R or R' comprises at least 3 carbon atoms. In some embodiments, at least one R or R' comprises at least 4 carbon atoms.

[0221] In some embodiments, at least one R or R' comprises a substituent selected from the group consisting of alkyl, cycloalkyl, silyl, germyl, aryl, heteroaryl, and combinations thereof.

[0222] In some embodiments, R and R' are joined or fused to form a ring.

[0223] In some embodiments, moieties C and D together do not form a naphthalene.

[0224] In some embodiments, moieties C and D together form a naphthalene, and R C is not unsubstituted carbazole, 2,7-di-tert-butyl-carbazole, or 3,5-di-tert-butyl-carbazole.

[0225] In some embodiments, Z 2 is X 1 In some embodiments, Z 2 is X 2 In some embodiments, Z 2 is X 3 In some embodiments, Z 2 is X 4 Combine with.

[0226] In some embodiments, the metal is Ir.

[0227] In some embodiments, the metal is Pt.

[0228] In some embodiments, the substituent R * is selected from the group consisting of the structures in List A below: [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] (where (D)H indicates that the moiety can be either H or D).

[0229] In some embodiments, the ligand L A is selected from the group consisting of the structures in List 1 below: [ka] [ka] [ka] [ka] [ka] (In the formula, X1~X6 and X8~X 19 are each independently C or N; Y A , Y B , and Y C Each of the e , N.R. e , PR e , O, S, Se, C=O, S=O, SO2, CR e R f , SiR e R f , and GeR e R f selected from the group consisting of: Each R A1 , R B1 , R B2 , and R B3 independently represent one to the maximum possible number of substitutions, or no substitutions; Each R A1 , R B1 , R B2 , R B3 , R e , and R f are independently hydrogen or a substituent selected from the group consisting of the general substituents defined herein; any two substituents may be joined or fused to form a ring; and At least one R B2 or R B3 is a substituent R containing a carbocyclic or heterocyclic group * (It is).

[0230] Ligand L A In some embodiments, X is selected from List 1 8 is a carbon and is attached to the 5- or 6-membered N-containing ring at the top portion. In some embodiments, X 9 is a carbon and is attached to the 5- or 6-membered N-containing ring at the top portion. In some embodiments, X10 is a carbon and is attached to the 5- or 6-membered N-containing ring at the top portion. In some embodiments, X 11 is a carbon and is attached to the 5- or 6-membered N-containing ring at the top portion.

[0231] Ligand L A In some embodiments, X8 to X 19 In some such embodiments, one of X is C and is substituted with a group selected from the group consisting of the structures of List A as defined herein. 13 is C, substituted with a group selected from the group consisting of the structures of List A as defined herein.

[0232] Ligand L A In some embodiments, where X is selected from List 1, X is C and R contains at least one C atom. B1 In some such embodiments, R B1 contains at least two C atoms. In some such embodiments, R B1 contains at least 3 C atoms. In some such embodiments, R B1 contains at least four C atoms.

[0233] Ligand L A In some embodiments, where X is selected from List 1, X is C and R comprises a moiety selected from the group consisting of alkyl, partially or fully deuterated alkyl, cycloalkyl, partially or fully deuterated cycloalkyl, ether, and an electron-withdrawing group. B1 is replaced by

[0234] Ligand L A In some embodiments, where X is selected from List 1, X is C and R comprises a moiety selected from the group consisting of alkyl, partially or fully deuterated alkyl, cycloalkyl, partially or fully deuterated cycloalkyl, and ether. B1 is replaced by

[0235] Ligand L A is selected from List 1, X is C and R comprises a moiety selected from the group consisting of CH, CD, isopropyl, t-butyl, partially or fully deuterated isopropyl, partially or fully deuterated neopentyl, cyclohexane, partially or fully deuterated cyclohexane, OCH, and F. B1 is replaced by

[0236] Ligand L A In some embodiments, where X is selected from List 1, X is C and R comprises a moiety selected from the group consisting of CH, CD, t-butyl, fully deuterated t-butyl, and F. B1 is replaced by

[0237] Ligand L A In some embodiments, where X is selected from List 1, X is C and R comprises an electron-withdrawing group. B1 is replaced by

[0238] Ligand L A In some embodiments, X is C and R comprises an electron withdrawing group selected from EWG1 list as defined herein. B1 is replaced by

[0239] Ligand L A In some embodiments, X is C and R is or includes an electron withdrawing group from the EWG1 list as defined herein. B1 In some such embodiments, R B1 is or includes an electron withdrawing group from the EWG2 list as defined herein. In some such embodiments, R B1 is or includes an electron withdrawing group from the EWG3 list as defined herein. In some such embodiments, R B1 is or includes an electron withdrawing group from the EWG4 list as defined herein. B1is or comprises an electron withdrawing group from the Pi-EWG list as defined herein.

[0240] Ligand L A In some embodiments, where X is selected from List 1, X is C and R is F, CH, CD, or carbazole. B1 is replaced by

[0241] Ligand L A In some embodiments, X is C and R is CN or CD. B1 is replaced by

[0242] Ligand L A In some embodiments, where X is selected from List 1, X is C and R is a partially or fully fluorinated alkyl. B1 is replaced by

[0243] Ligand L A In some embodiments, where X is selected from List 1, X is C and R comprises a silyl or germyl group. B1 is replaced by

[0244] Ligand L A In some embodiments, X is C and R may be selected from List B as defined herein. B1 is replaced by

[0245] Ligand L A In some embodiments, where R is selected from List 1, A1 are linked to form a fused ring. In some such embodiments, the fused ring can be benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, imidazole-derived carbene, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole, or triazole. In some such embodiments, the fused ring can be benzene.

[0246] In some embodiments, Y Ais NR e In some such embodiments, R e is or includes a structure of Formula II or Formula IIA. In such embodiments, all embodiments relating to Formula II or Formula IIA are equally applicable herein. In some embodiments, Y B and Y C Each of is independently O.

[0247] Ligand L A In some embodiments, Y is selected from List 1 A is NR e R e may be selected from the group consisting of the following structures (List A2): [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] (where the dotted line connects to N).

[0248] Ligand L A In some embodiments, where R is selected from List 1, A1 , R B1 , R B2 , or R B3 is selected from the group consisting of the general substituents defined herein.A In some embodiments, where R is selected from List 1, A1 , R B1 , R B2 , or R B3 is selected from the group consisting of preferred general substituents defined herein. A In some embodiments, where R is selected from List 1, A1 , R B1 , R B2 , or R B3 is partially or fully deuterated. In some embodiments, at least one R A1 is partially or fully deuterated. In some embodiments, at least one R B1 is partially or fully deuterated. In some embodiments, at least one R B2 is partially or fully deuterated. In some embodiments, at least one R B3 is partially or fully deuterated.

[0249] Ligand L A In some embodiments, where R is selected from List 1, A1 is or includes an electron withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R A1 is or includes an electron withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R A1 is or includes an electron withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R A1 is or includes an electron withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R A1 is or comprises an electron withdrawing group from the Pi-EWG list as defined herein.

[0250] Ligand L A In some embodiments, where R is selected from List 1,B1 is or includes an electron withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R B1 is or includes an electron withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R B1 is or includes an electron withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R B1 is or includes an electron withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R B1 is or comprises an electron withdrawing group from the Pi-EWG list as defined herein.

[0251] Ligand L A In some embodiments, where R is selected from List 1, B2 is or includes an electron withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R B2 is or includes an electron withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R B2 is or includes an electron withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R B2 is or includes an electron withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R B2 is or comprises an electron withdrawing group from the Pi-EWG list as defined herein.

[0252] Ligand L A In some embodiments, where R is selected from List 1, B3 is or includes an electron withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R B3is or includes an electron withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R B3 is or includes an electron withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R B3 is or includes an electron withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R B3 is or comprises an electron withdrawing group from the Pi-EWG list as defined herein.

[0253] In some embodiments, the ligand L A is selected from the group consisting of the structures in List 2 below: [ka] [ka] [ka] [ka] [ka] (In the formula, X is C or N; Y A , Y B , and Y C Each of the e , N.R. e , PR e , O, S, Se, C=O, S=O, SO2, CR e R f , SiR e R f , and GeR e R f selected from the group consisting of: Each R A1 , R B1 , R B2 , and R B3independently represent one to the maximum possible number of substitutions, or no substitutions; Each R A1 , R B1 , R B2 , R B3 , R e , and R f are independently hydrogen or a substituent selected from the group consisting of the general substituents defined herein; any two substituents may be joined or fused to form a ring; and At least one R B2 or R B3 is a substituent R containing a carbocyclic or heterocyclic group * (It is).

[0254] Ligand L A In some embodiments, where R is selected from List 2, A1 are linked to form a fused ring. In some such embodiments, the fused ring can be benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, imidazole-derived carbene, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole, or triazole. In some such embodiments, the fused ring can be benzene.

[0255] Ligand L A In some embodiments, where X is selected from List 2, X is carbon and R is selected from the group consisting of the structures of List A as defined herein. B2 may be substituted with

[0256] Ligand L A In some embodiments, where R is selected from List 2, the carbon atom para to the carbon linked to the N-containing moiety above is an R B1 In some such embodiments, R B1 contains at least two C atoms. In some such embodiments, R B1 contains at least 3 C atoms. In some such embodiments, R B1contains at least four C atoms.

[0257] Ligand L A In some embodiments, where R is selected from List 2, the carbon atom para to the carbon linked to the N-containing moiety above is selected from the group consisting of alkyl, partially or fully deuterated alkyl, cycloalkyl, partially or fully deuterated cycloalkyl, ether, and an electron withdrawing group. B1 is replaced by

[0258] Ligand L A In some embodiments, where R is selected from List 2, the carbon atom para to the carbon linked to the N-containing moiety above is an R containing a moiety selected from the group consisting of alkyl, partially or fully deuterated alkyl, cycloalkyl, partially or fully deuterated cycloalkyl, and ether. B1 is replaced by

[0259] Ligand L A In some embodiments, where R is selected from List 2, the carbon atom para to the carbon linked to the N-containing moiety above is selected from the group consisting of CH, CD, isopropyl, t-butyl, partially or fully deuterated isopropyl, partially or fully deuterated neopentyl, cyclohexane, partially or fully deuterated cyclohexane, OCH, and F. B1 is replaced by

[0260] Ligand L A In some embodiments, where R is selected from List 2, the carbon atom para to the carbon linked to the N-containing moiety above is selected from the group consisting of CH, CD, t-butyl, fully deuterated t-butyl, and F. B1 is replaced by

[0261] Ligand L A In some embodiments, where R is selected from List 2, the carbon atom para to the carbon linked to the N-containing moiety above is R B1is replaced by

[0262] Ligand L A In some embodiments, where R is selected from List 2, the carbon atom para to the carbon linked to the N-containing moiety above is selected from List 1 as defined herein. B1 is replaced by

[0263] Ligand L A In some embodiments, where R is selected from List 2, the carbon atom para to the carbon linked to the N-containing moiety above is an R that is or includes an electron withdrawing group from the EWG1 list as defined herein. B1 In some such embodiments, R B1 is or includes an electron withdrawing group from the EWG2 list as defined herein. In some such embodiments, R B1 is or includes an electron withdrawing group from the EWG3 list as defined herein. In some such embodiments, R B1 is or includes an electron withdrawing group from the EWG4 list as defined herein. In some such embodiments, R B1 is or comprises an electron withdrawing group from the Pi-EWG list as defined herein.

[0264] Ligand L A In some embodiments, where R is selected from List 2, the carbon atom para to the carbon connected to the N-containing moiety above is F, CH, CD, or carbazole. B1 is replaced by

[0265] Ligand L A In some embodiments, where R is selected from List 2, the carbon atom para to the carbon linked to the N-containing moiety above is C-N or C-D. B1 is replaced by

[0266] Ligand L AIn some embodiments where R is selected from List 2, the carbon atom para to the carbon linked to the N-containing moiety above is a partially or fully fluorinated alkyl, R B1 is replaced by

[0267] Ligand L A In some embodiments, where R is selected from List 2, the carbon atom para to the carbon connected to the N-containing moiety above is an R containing a silyl or germyl group. B1 is replaced by

[0268] Ligand L A In some embodiments, where R is selected from List 2, the carbon atom para to the carbon connected to the N-containing moiety above is selected from the list defined herein. B1 is replaced by

[0269] Ligand L A In some embodiments, Y is selected from List 2 A is the NR in the structure e In some such embodiments, R e is or includes a structure of Formula II or Formula IIA. In such embodiments, all embodiments relating to Formula II or Formula IIA are equally applicable here. In some embodiments, X is C in the structure. In some embodiments, X is N in the structure. In some embodiments, Y B and Y C Each of is independently O in the structure.

[0270] Ligand L A In some embodiments, Y is selected from List 2 A is NR e R e may be selected from the group consisting of the structures of List A2 defined herein.

[0271] Ligand L A In some embodiments, where R is selected from List 2, A1 , R B1 , RB2 , or R B3 is selected from the group consisting of the general substituents defined herein. A In some embodiments, where R is selected from List 1, A1 , R B1 , R B2 , or R B3 is selected from the group consisting of preferred general substituents defined herein. A In some embodiments, where R is selected from List 1, A1 , R B1 , R B2 , or R B3 is partially or fully deuterated. In some embodiments, at least one R A1 is partially or fully deuterated. In some embodiments, at least one R B1 is partially or fully deuterated. In some embodiments, at least one R B2 is partially or fully deuterated. In some embodiments, at least one R B3 is partially or fully deuterated.

[0272] Ligand L A In some embodiments, where R is selected from List 2, A1 is or includes an electron withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R A1 is or includes an electron withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R A1 is or includes an electron withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R A1 is or includes an electron withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R A1 is or comprises an electron withdrawing group from the Pi-EWG list as defined herein.

[0273] Ligand L A In some embodiments, where R is selected from List 2, B1 is or includes an electron withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R B1 is or includes an electron withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R B1 is or includes an electron withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R B1 is or includes an electron withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R B1 is or comprises an electron withdrawing group from the Pi-EWG list as defined herein.

[0274] Ligand L A In some embodiments, where R is selected from List 2, B2 is or includes an electron withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R B2 is or includes an electron withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R B2 is or includes an electron withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R B2 is or includes an electron withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R B2 is or comprises an electron withdrawing group from the Pi-EWG list as defined herein.

[0275] Ligand L A In some embodiments, where R is selected from List 2, B3is or includes an electron withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R B3 is or includes an electron withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R B3 is or includes an electron withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R B3 is or includes an electron withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R B3 is or comprises an electron withdrawing group from the Pi-EWG list as defined herein.

[0276] In some embodiments, the ligand L A L Ai (R H )(R I )(R J )(R K )(R L ), L Ai’ (R H )(R I )(R J )(R K’ )(R L ), and L Ai’’ (R H )(R I )(R J )(R K’’ )(R L ), where i is an integer from 1 to 10, i' is an integer from 11 to 37, and i'' is an integer from 38 to 43; H , R I , R J , and R K are each independently selected from V1 to V192; R L is selected from O1 to O328; R K’ is selected from V1 to V180; R K’’ is selected from V1 to V178; and L Ai (R H )(R I )(R J )(R K )(RL ), L Ai’ (R H )(R I )(R J )(R K’ )(R L ), and L Ai’’ (R H )(R I )(R J )(R K’’ )(R L ) are defined in Listing 3 below: [ka] [ka] [ka] [ka] wherein O1 to O328 are as defined in List A as defined herein; V1 through V192 are defined in List B below: [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0277] In some embodiments, the ligand L A is defined in Listing 3a below. A’n (R H )(R I )(R J )(R K )(R L ) and L A’n’ (R H )(R I )(R J )(R K )(R K’’ )(R L ), wherein n is an integer from 1 to 12, n' is an integer from 13 to 26, and R H , R I , R J , and R K are each independently selected from V1 to V192; R L is selected from O1 to O328; R K’’ is selected from V1 to V178; L A’n (R H )(R I )(R J )(R K )(R L ) is L A’1 (V1)(V1)(V1)(V1)(O1)~L A’12 (V192)(V192)(V192)(V192)(O328), L A’n’ (R H )(R I )(R J )(R K )(R K’’ )(R L ) is L A’13 (V1)(V1)(V1)(V1)(V1)(O1)~L A’26 Selected from: (V192)(V192)(V192)(V192)(V178)(O328): [ka] [ka] wherein V1 to V192 are as defined in List B defined herein; O1 to O328 are defined in List A herein).

[0278] In some embodiments, the compound is M(L A ) p (L B ) q (L C ) r wherein L B and L C are each a bidentate ligand; 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.

[0279] In some embodiments, the compound is 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 wherein L A , L B , and L C are different from each other.

[0280] In some embodiments, L B is a substituted or unsubstituted phenylpyridine, L C is a substituted or unsubstituted acetylacetonate.

[0281] In some embodiments, the compound is Pt(L A )(L B ) has the formula: L A and L B may be the same or different.

[0282] In some embodiments, L A and L B are linked to form a tetradentate ligand.

[0283] In some embodiments, L B and L C are each independently selected from the group consisting of the structures in List 4 below: [ka] [ka] (In the formula: T is selected from the group consisting of B, Al, Ga, and In; K 1’ is a single bond, O, S, NR e , PR e , B.R. e , C.R. e R f , and SiR e R f selected from the group consisting of: Y 1 ~Y 13 each is independently selected from the group consisting of C and N; Y' is BR e , B.R. e R f , N.R. 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 selected from the group consisting of: R e and R f can be fused or linked to form a ring; Each R a , R b , R c , and R dindependently represent one to the maximum number of substitutions allowed, or no substitutions; R a1 , R b1 , R c1 , R d1 , R a , R b , R c , R d , R e , and R f each is independently hydrogen or a substituent selected from the group consisting of deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, selenyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; R a1 , R b1 , R c1 , R d1 , R a , R b , R c , and R d Any two substituents of can be fused or linked to form a ring or to form a multidentate ligand).

[0284] In some embodiments, L B and L C are each independently selected from the group consisting of the structures in List 5 below: [ka] [ka] [ka] [ka] [ka] (In the formula, R a ', R b ', R c ', R d ', and R e each independently represents zero substitution, one substitution, or up to the maximum number of substitutions allowed for its associated ring; R a1 , R b1 , R c1 , R a ', R b ', R c ', R d ', and R e each independently represents a substituent selected from the group consisting of hydrogen, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, selenyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; R a1 , R b1 , R c1 , R a ', R b ', R c ', R d ', and R e The two substituents in may be fused or linked to form a ring or to form a multidentate ligand).

[0285] In some embodiments, L B teeth, [ka] wherein the variables are as defined above. In some embodiments, Y 1 ~Y 4 Each of Y is independently carbon. 1 ~Y 4 At least one of Y is N. In some embodiments, 1 ~Y4 Exactly one of Y 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.

[0286] In some embodiments, Y 1 is carbon and R a1 In some such embodiments, R a1 may be selected from the group consisting of general substituents defined herein. In some such embodiments, R a1 may be selected from the group consisting of preferred general substituents defined herein. In some such embodiments, R a1 is tertiary alkyl, silyl, or germyl. In some such embodiments, R a1 is a tertiary alkyl. In some embodiments, Y 2 is carbon and R a2 In some such embodiments, R a2 may be selected from the group consisting of general substituents defined herein. In some such embodiments, R a2 may be selected from the group consisting of preferred general substituents defined herein. In some such embodiments, R a2 is tertiary alkyl, silyl, or germyl. In some such embodiments, R a2 is a tertiary alkyl. In some embodiments, Y 3 is carbon and R a3 In some such embodiments, R a3 may be selected from the group consisting of general substituents defined herein. In some such embodiments, R a3 may be selected from the group consisting of preferred general substituents defined herein. In some such embodiments, R a3 is tertiary alkyl, silyl, or germyl. In some such embodiments, Ra3 is a tertiary alkyl. In some embodiments, Y 4 is carbon and R a4 In some such embodiments, R a4 may be selected from the group consisting of general substituents defined herein. In some such embodiments, R a4 may be selected from the group consisting of preferred general substituents defined herein. In some such embodiments, R a4 is tertiary alkyl, silyl, or germyl. In some such embodiments, R a4 is a tertiary alkyl.

[0287] In some embodiments, Y 1 ~Y 3 is C and Y 4 is N and Y 3 R bonded to a3 is tertiary alkyl, silyl, or germyl. In some embodiments, Y 1 ~Y 3 is C and Y 4 is N and Y 2 R bonded to a2 is tertiary alkyl, silyl or germyl.

[0288] In some embodiments, R b At least one of R is tertiary alkyl, silyl, or germyl. In some embodiments, the tertiary alkyl is tert-butyl. In some embodiments, R a and R b At least one pair of these is bonded or fused to form a ring.

[0289] In some embodiments, R b1 is attached to C1 (carbon atom). In some such embodiments, R b1 may be selected from the group consisting of general substituents defined herein. In some such embodiments, R b1may be selected from the group consisting of preferred general substituents defined herein. In some such embodiments, R b1 is tertiary alkyl, silyl, or germyl. In some such embodiments, R b1 is a tertiary alkyl. In some embodiments, the tertiary alkyl is tert-butyl. In some embodiments, R b2 is attached to C2 (carbon atom). In some such embodiments, R b2 may be selected from the group consisting of general substituents defined herein. In some such embodiments, R b2 may be selected from the group consisting of preferred general substituents defined herein. In some such embodiments, R b2 is tertiary alkyl, silyl, or germyl. In some such embodiments, R b2 is a tertiary alkyl. In some embodiments, the tertiary alkyl is tert-butyl. In some embodiments, R b3 is attached to C3 (carbon atom). In some such embodiments, R b3 may be selected from the group consisting of general substituents defined herein. In some such embodiments, R b3 may be selected from the group consisting of preferred general substituents defined herein. In some such embodiments, R b3 is tertiary alkyl, silyl, or germyl. In some such embodiments, R b3 is a tertiary alkyl. In some embodiments, the tertiary alkyl is tert-butyl. In some embodiments, R b4 is attached to C4 (carbon atom). In some such embodiments, R b4 may be selected from the group consisting of general substituents defined herein. In some such embodiments, R b4 may be selected from the group consisting of preferred general substituents defined herein. In some such embodiments, R b4is tertiary alkyl, silyl, or germyl. In some such embodiments, R b4 is a tertiary alkyl. In some embodiments, the tertiary alkyl is tert-butyl.

[0290] In some embodiments, 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 formula Ir(L A )2(L Cj-II ) and L A L A1 (V1)(V1)(V1)(V1)(O1)~L A11 (V192)(V192)(V192)(V192)(O328), L A12 (V1)(V1)(V1)(V1)(O1)~L A37 (V192)(V192)(V192)(V180)(O328), L A38 (V1)(V1)(V1)(V1)(O1)~L A43 (V192)(V192)(V192)(V178)(O328), L A’1 (V1)(V1)(V1)(V1)(O1)~L A’12 (V192)(V192)(V192)(V192)(O328), and L A’13 (V1)(V1)(V1)(V1)(V1)(O1)~L A’26 as described herein, including (V192)(V192)(V192)(V192)(V178)(O328); k is an integer from 1 to 543, and each L Bk is the structure defined in Listing 6 below: [ka] [ka] [ka]

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[0291] In some embodiments, the compound is L Bk is selected from the group consisting of only compounds in which L corresponds to one of the following: 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 B357 , 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 .

[0292] In some embodiments, the compound is LBk is selected from the group consisting of only compounds in which L corresponds to one of the following: 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 .

[0293] In some embodiments, the compound is L Cj-I or L Cj-II The compound is selected from the group consisting of only compounds having a ligand, and the corresponding R 201 and R 202 is defined to be one of the following structures: D1 , R D3 , R D4 , R D5 , R D9 , R D10 , R D17 , R D18 , R D20 , R D22 , R D37 , R D40 , R D41 , R D42 , R D43 , R D48 , R D49 , R D50 , R D54 , R D55 , R D58 , R D59 , R D78 , R D79 , R D81 , R D87 , R D88 , R D89 , R D93 , R D116 , R D117 , R D118 , R D119 , R D120 , R D133 , R D134 , R D135 , R D136 , RD143 , 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 .

[0294] In some embodiments, the compound is L Cj-I or L Cj-II The compound is selected from the group consisting of only compounds having a ligand, and the corresponding R 201 and R 202 is defined to be one selected from the following structures: 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 , RD193 , 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 .

[0295] In some embodiments, the compound is L Cj-I The ligand is selected from the group consisting of only compounds having one of the structures in list 8 below: [ka]

[0296] In some embodiments, the compound is 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 structures in List 1, List 2, and List 3; L B List 4, List 5, and List 6 (L Bk ) and L C is the L defined in Listing 7 Cj-I and L Cj-II The structure is selected from the group consisting of:

[0297] In some embodiments, L A is selected from the group consisting of structures in List 1, and L B L BkIn some embodiments, L is selected from the group consisting of A is selected from the group consisting of structures in List 2, and L B L Bk In some embodiments, L is selected from the group consisting of A is selected from List 3 as defined herein, and L B is L where k is an integer between 1 and 543 Bk In some embodiments, L is selected from the group consisting of A is selected from List 1 as defined herein, and L C is L where j is an integer between 1 and 1416. Cj-I and L Cj-II The structure is selected from the group consisting of:

[0298] In some embodiments, the compound is Ir(L A1 (V1)(V1)(V1)(V1)(O1))3~Ir(L A11 (V192)(V192)(V192)(V192)(O328))3 Ai (R H )(R I )(R J )(R K )(R L ))3, Ir(L A1 (V1)(V1)(V1)(V1)(O1))(L B1 )2~Ir(L A11 (V192)(V192)(V192)(V192)(O328))(L B543 )2 of the formula Ir(L Ai (R H )(R I )(R J )(R K )(R L ))(L Bk )2, Ir(L A1 (V1)(V1)(V1)(V1)(O1))2(L B1 )~Ir(L A11 (V192)(V192)(V192)(V192)(O328))2(L B543 ) consisting of compounds of the formula Ir(L Ai (R H)(R I )(R J )(R K )(R L ))2(L Bk )、Ir(L A1 (V1)(V1)(V1)(V1)(O1))2(L C1-I )~Ir(L A11 (V192)(V192)(V192)(V192)(O328))2(L C1416-I ) of which the root is Ir(L Ai (R H )(R I )(R J )(R K )(R L ))2(L Cj-I )、Ir(L A1 (V1)(V1)(V1)(V1)(O1))2(L C1-II )~Ir(L A11 (V192)(V192)(V192)(V192)(O328))2(L C1416-II ) of which the root is Ir(L Ai (R H )(R I )(R J )(R K )(R L ))2(L Cj-II )、Ir(L A1 (V1)(V1)(V1)(V1)(O1))(L B1 )(L C1-I )~Ir(L A11 (V192)(V192)(V192)(V192)(O328))(L B543 )(L C1416-I ) of which the root is Ir(L Ai (R H )(R I )(R J )(R K )(R L ))(L Bk )(L Cj-I ) and Ir(L A1 (V1)(V1)(V1)(V1)(O1))(L B1 )(L C1-II )~Ir(L A11 (V192)(V192)(V192)(V192)(O328))(L B543)(L C1416-II ) consisting of compounds of the formula Ir(L Ai (R H )(R I )(R J )(R K )(R L )(L Bk )(L Cj-II ), and L Ai (R H )(R I )(R J )(R K )(R L ), L Bk , and L Cj-I and L Cj-II are all defined herein.

[0299] In some embodiments, the compound is Ir(L A12 (V1)(V1)(V1)(V1)(O1))3~Ir(L A37 (V192)(V192)(V192)(V180)(O328))3 Ai’ (R H )(R I )(R J )(R K’ )(R L ))3, Ir(L A12 (V1)(V1)(V1)(V1)(O1))(L B1 )2~Ir(L A37 (V192)(V192)(V192)(V180)(O328))(L B543 )2 of the formula Ir(L Ai’ (R H )(R I )(R J )(R K’ )(R L ))(L Bk )2, Ir(L A12 (V1)(V1)(V1)(V1)(O1))2(L B1 )~Ir(L A37 (V192)(V192)(V192)(V180)(O328))2(L B543 ) consisting of compounds of the formula Ir(L Ai’ (R H )(R I)(R J )(R K’ )(R L ))2(L Bk )、Ir(L A12 (V1)(V1)(V1)(V1)(O1))2(L C1-I )~Ir(L A37 (V192)(V192)(V192)(V180)(O328))2(L C1416-I ) of which the root is Ir(L Ai’ (R H )(R I )(R J )(R K’ )(R L ))2(L Cj-I )、Ir(L A12 (V1)(V1)(V1)(V1)(O1))2(L C1-II )~Ir(L A37 (V192)(V192)(V192)(V180)(O328))2(L C1416-II ) of which the root is Ir(L Ai’ (R H )(R I )(R J )(R K’ )(R L ))2(L Cj-II )、Ir(L A12 (V1)(V1)(V1)(V1)(O1))(L B1 )(L C1-I )~Ir(L A37 (V192)(V192)(V192)(V180)(O328))(L B543 )(L C1416-I ) of which the root is Ir(L Ai’ (R H )(R I )(R J )(R K’ )(R L ))(L Bk )(L Cj-I ) and Ir(L A12 (V1)(V1)(V1)(V1)(O1))(L B1 )(L C1-II )~Ir(L A37 (V192)(V192)(V192)(V180)(O328))(L B543 )(L C1416-II) consisting of compounds of the formula Ir(L Ai’ (R H )(R I )(R J )(R K’ )(R L ))(L Bk )(L Cj-II ), and L Ai’ (R H )(R I )(R J )(R K’ )(R L ), L Bk , and L Cj-I and L Cj-II are all defined herein.

[0300] In some embodiments, the compound is Ir(L A38 (V1)(V1)(V1)(V1)(O1))3~Ir(L A43 (V192)(V192)(V192)(V178)(O328))3 Ai’’ (R H )(R I )(R J )(R K’’ )(R L ))3, Ir(L A38 (V1)(V1)(V1)(V1)(O1))(L B1 )2~Ir(L A43 (V192)(V192)(V192)(V178)(O328))(L B543 )2 of the formula Ir(L Ai’’ (R H )(R I )(R J )(R K’’ )(R L ))(L Bk )2, Ir(L A38 (V1)(V1)(V1)(V1)(O1))2(L B1 )~Ir(L A43 (V192)(V192)(V192)(V178)(O328))2(L B543 ) consisting of compounds of the formula Ir(L Ai’’ (R H )(R I )(RJ )(R K’’ )(R L ))2(L Bk )、Ir(L A38 (V1)(V1)(V1)(V1)(O1))2(L C1-I )~Ir(L A43 (V192)(V192)(V192)(V178)(O328))2(L C1416-I ) of which the root is Ir(L Ai’’ (R H )(R I )(R J )(R K’’ )(R L ))2(L Cj-I )、Ir(L A38 (V1)(V1)(V1)(V1)(O1))2(L C1-II )~Ir(L A43 (V192)(V192)(V192)(V178)(O328))2(L C1416-II ) of which the root is Ir(L Ai’’ (R H )(R I )(R J )(R K’’ )(R L ))2(L Cj-II )、Ir(L A38 (V1)(V1)(V1)(V1)(O1))(L B1 )(L C1-I )~Ir(L A43 (V192)(V192)(V192)(V178)(O328))(L B543 )(L C1416-I ) of which the root is Ir(L Ai’’ (R H )(R I )(R J )(R K’’ )(R L ))(L Bk )(L Cj-I ) and Ir(L A38 (V1)(V1)(V1)(V1)(O1))(L B1 )(L C1-II )~Ir(L A43 (V192)(V192)(V192)(V178)(O328))(L B543 )(L C1416-II) consisting of compounds of the formula Ir(L Ai’’ (R H )(R I )(R J )(R K’’ )(R L ))(L Bk )(L Cj-II ), and L Ai’’ (R H )(R I )(R J )(R K’’ )(R L ), L Bk , and L Cj-I and L Cj-II are all defined herein.

[0301] In some embodiments, the compound is Ir(L A’1 (V1)(V1)(V1)(V1)(O1))3~Ir(L A’12 (V192)(V192)(V192)(V192)(O328))3 A’n (R H )(R I )(R J )(R K )(R L ))3, Ir(L A’1 (V1)(V1)(V1)(V1)(O1))(L B1 )2~Ir(L A’12 (V192)(V192)(V192)(V192)(O328))(L B543 )2 of the formula Ir(L A’n (R H )(R I )(R J )(R K )(R L ))(L Bk )2, Ir(L A’1 (V1)(V1)(V1)(V1)(O1))2(L B1 )~Ir(L A’12 (V192)(V192)(V192)(V192)(O328))2(L B543 ) consisting of compounds of the formula Ir(L A’n (R H )(R I )(RJ )(R K )(R L ))2(L Bk )、Ir(L A’1 (V1)(V1)(V1)(V1)(O1))2(L C1-I )~Ir(L A’12 (V192)(V192)(V192)(V192)(O328))2(L C1416-I ) of which the root is Ir(L A’n (R H )(R I )(R J )(R K )(R L ))2(L Cj-I )、Ir(L A’1 (V1)(V1)(V1)(V1)(O1))2(L C1-II )~Ir(L A’12 (V192)(V192)(V192)(V192)(O328))2(L C1416-II ) of which the root is Ir(L A’n (R H )(R I )(R J )(R K )(R L ))2(L Cj-II )、Ir(L A’1 (V1)(V1)(V1)(V1)(O1))(L B1 )(L C1-I )~Ir(L A’12 (V192)(V192)(V192)(V192)(O328))(L B543 )(L C1416-I ) of which the root is Ir(L A’n (R H )(R I )(R J )(R K )(R L ))(L Bk )(L Cj-I )、Ir(L A’1 (V1)(V1)(V1)(V1)(O1))(L B1 )(L C1-II )~Ir(L A’12 (V192)(V192)(V192)(V192)(O328))(L B543 )(L C1416-II) consisting of compounds of the formula Ir(L A’n (R H )(R I )(R J )(R K )(R L ))(L Bk )(L Cj-II ), and L A’n (R H )(R I )(R J )(R K )(R L ), L Bk , and L Cj-I and L Cj-II are all defined herein.

[0302] In some embodiments, the compound is Ir(L A’13 (V1)(V1)(V1)(V1)(V1)(O1))3~Ir(L A’26 (V192)(V192)(V192)(V192)(V178)(O328)) A’n’ (R H )(R I )(R J )(R K )(R K’’ )(R L ))3, Ir(L A’13 (V1)(V1)(V1)(V1)(V1)(O1))(L B1 )2~Ir(L A’26 (V192)(V192)(V192)(V192)(V178)(O328))(L B543 )2 of the formula Ir(L A’n’ (R H )(R I )(R J )(R K )(R K’’ )(R L ))(L Bk )2, Ir(L A’13 (V1)(V1)(V1)(V1)(V1)(O1))2(L B1 )~Ir(L A’26 (V192)(V192)(V192)(V192)(V178)(O328))2(L B543) consisting of compounds of the formula Ir(L A’n’ (R H )(R I )(R J )(R K )(R K’’ )(R L ))2(L Bk ), Ir(L A’13 (V1)(V1)(V1)(V1)(V1)(O1))2(L C1-I )~Ir(L A’26 (V192)(V192)(V192)(V192)(V178)(O328))2(L C1416-I ) consisting of compounds of the formula Ir(L A’n’ (R H )(R I )(R J )(R K )(R K’’ )(R L ))2(L Cj-I ), Ir(L A’13 (V1)(V1)(V1)(V1)(V1)(O1))2(L C1-II )~Ir(L A’26 (V192)(V192)(V192)(V192)(V178)(O328))2(L C1416-II ) consisting of compounds of the formula Ir(L A’n’ (R H )(R I )(R J )(R K )(R K’’ )(R L ))2(L Cj-II ), Ir(L A’13 (V1)(V1)(V1)(V1)(V1)(O1))(L B1 )(L C1-I )~Ir(L A’26 (V192)(V192)(V192)(V192)(V178)(O328))(L B543 )(L C1416-I ) consisting of compounds of the formula Ir(L A’n’ (R H )(R I )(R J )(R K )(R K’’ )(R L ))(L Bk )(L Cj-I), IrL A’13 (V1)(V1)(V1)(V1)(V1)(O1))(L B1 )(L C1-II )~Ir(L A’26 (V192)(V192)(V192)(V192)(V178)(O328))(L B543 )(L C1416-II ) consisting of compounds of the formula Ir(L A’n’ (R H )(R I )(R J )(R K )(R K’’ )(R L ))(L Bk )(L Cj-II ), and L A’n’ (R H )(R I )(R J )(R K )(R K’’ )(R L ), L Bk , and L Cj-I and L Cj-II are all defined herein.

[0303] In some embodiments, the compound is selected from the group consisting of the structures in List 9 below: [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

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[0304] In some embodiments, the compound is [ka] may be.

[0305] In some embodiments, the first ligand L comprises a structure of Formula I described herein. A In some embodiments, the compound having the first ligand L of formula I described herein is partially or fully deuterated. In some embodiments, the compound is fully deuterated. In some embodiments, the compound having the first ligand L of formula I described herein is A 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, percent deuterated has its ordinary meaning and includes the percent of all available hydrogen atoms (e.g., positions that are hydrogen or deuterium) in the compound that are occupied by deuterium atoms. In some embodiments, the carbon atoms comprising the ring coordinated to the metal M are fully or partially deuterated. In some embodiments, the carbon atoms comprised by a polycyclic ring system coordinated to the metal M are fully or partially deuterated. In some embodiments, the substituents attached to a monocyclic or polycyclic fused ring system coordinated to the metal M are fully or partially deuterated.

[0306] In some embodiments, the compounds of Formula I have a full width at half maximum (FWHM) emission at room temperature of 50 nm, 45 nm, 40 nm, 35 nm, 30 nm, 25 nm, 20 nm, 15 nm, 10 nm, or 5 nm or less. A narrower FWHM means better color purity for OLED display applications.

[0307] As defined above, M(L A ) p (L B )q (L C ) r In some embodiments of the heteroleptic compound having the formula A is the first substituent R I and the first substituent R I is the ligand L A Among all atoms in the metal M, the first atom aI is the atom furthest from the metal M. In addition, the ligand L B is, if present, the second substituent R II and a second substituent R II is the ligand L B Among all atoms in the metal complex, the first atom a-II is the atom furthest from the metal M. Furthermore, the ligand L C If present, the third substituent R III and a third substituent R III is the ligand L C Among all atoms in the metal complex, the first atom a-III is the atom farthest from the metal M.

[0308] In such heteroleptic compounds, the vector 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 aI, and the vector V D1 is the first substituent R I The value D represents the linear distance between the metal M and the first atom aI in 1 V D2 represents the direction from the metal M to the first atom a-II, and the vector V D2 is the second substituent R II The value D represents the linear distance between the metal M and the first atom a-II in 2 V D3 represents the direction from the metal M to the first atom a-III, and the vector V D3 is the third substituent R III The value D represents the linear distance between the metal M and the first atom a-III in 3 It has.

[0309] In such heteroleptic compounds, a sphere with radius r is defined, the center of which is the metal M, and the radius r is determined by the number of substituents R I , R II and R III is the smallest radius that allows enclosing all atoms in the compound that are not part of D 1 , D 2 , and D 3 At least one of D is at least 1.5 Å greater than the radius r. 1 , D 2 , and D 3 At least one of D is at least 2.9 Å, 3.0 Å, 4.3 Å, 4.4 Å, 5.2 Å, 5.9 Å, 7.3 Å, 8.8 Å, 10.3 Å, 13.1 Å, 17.6 Å, or 19.1 Å greater than the radius r. 1 , D 2 , and D 3 At least two of the above are at least 1.5 Å, 2.9 Å, 3.0 Å, 4.3 Å, 4.4 Å, 5.2 Å, 5.9 Å, 7.3 Å, 8.8 Å, 10.3 Å, 13.1 Å, 17.6 Å, or 19.1 Å larger than the radius r.

[0310] In some embodiments of such heteroleptic compounds, the compound has a transition dipole moment axis and a vector V D1 , V D2 , and V D3 An angle is defined between the transition dipole moment axis and the vector V D1 , V D2 , and V D3 At least one of the angles between the transition dipole moment axis and the vector V is less than 40°. D1 , V D2 , and V D3 At least one of the angles between the transition dipole moment axis and the vector V is less than 30°, 20°, 15°, or 10°. D1 , V D2 , and V D3 At least two of the angles between the transition dipole moment axis and the vector V are less than 20°.D1 , V D2 , and V D3 At least two of the angles between are less than 15° or 10°.

[0311] In some embodiments, the transition dipole moment axis and the vector V D1 , V D2 , and V D3 All three angles between the transition dipole moment axis and the vector V are less than 20°. D1 , V D2 , and V D3 All three angles between are less than 15° or 10°.

[0312] In some embodiments of such heteroleptic compounds, the compounds have a vertical dipole ratio (VDR) of 0.33 or less. In some embodiments of such heteroleptic compounds, the compounds have a VDR of 0.30, 0.25, 0.20, or 0.15 or less.

[0313] Those skilled in the art will easily understand the meaning of the terms transition dipole moment axis of a compound and vertical dipole ratio of a compound. Nevertheless, 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. U.S. Patent No. 10,672,997 discusses the horizontal dipole ratio (HDR) of a compound, not VDR. However, those skilled in the art will easily understand that VDR=1-HDR.

[0314] In some embodiments, the compound can be an emissive dopant. In some embodiments, the compound can generate luminescence through phosphorescence, fluorescence, thermally activated delayed fluorescence, triplet-triplet annihilation, or a combination of these processes. In some embodiments, the emissive dopant can be a racemic mixture or enriched in one enantiomer. In some embodiments, the compound can have different stereoisomers, such as fac and mer. The compound refers to both 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). When there are multiple ligands coordinated to the metal, in some embodiments, the ligands can all be the same. In other embodiments, at least one ligand is different from the other ligands. In some embodiments, all ligands can be different from all other ligands. This is also true in embodiments where a ligand coordinated to a metal can be linked to other ligands coordinated to that metal to form a tridentate, tetradentate, pentadentate, or hexadentate ligand. Thus, when coordinating ligands are linked together, in some embodiments, all of the ligands can be the same, and at least one of the linked ligands can be different from the others in some other embodiments.

[0315] In yet another aspect of the present disclosure, a formulation comprising the novel compound disclosed herein is described. The formulation may comprise one or more components selected from the group consisting of a solvent, an emitter, a host, a hole injection material, a hole transport material, an electron blocking material, a hole blocking material, and an electron transport material disclosed herein.

[0316] The present disclosure encompasses any chemical structure comprising the novel compounds of the present disclosure, or monovalent or polyvalent variants thereof. In other words, the compounds of the present invention, or monovalent or polyvalent variants thereof, 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 known as macromolecules). As used herein, a "monovalent variant of a compound" refers to a moiety identical to the compound except that one hydrogen has been removed and replaced with a bond to the remainder of the chemical structure. As used herein, a "polyvalent variant of a compound" refers to a moiety identical to the compound except that two or more hydrogens have been removed and replaced with bonds to the remainder of the chemical structure. In the example of a supramolecule, the compounds of the present invention can also be incorporated into a supramolecular complex without a covalent bond. When used in this context, a statement that structure A includes a B moiety means that structure A includes a structure of B moiety that does not include an H atom or D atom that can be bonded to the B moiety. This is because at least one H or D on a given substructure must be substituted to become a substituent so that the B substructure can become part of structure A, and one or more H or D on a given B substructure can be further substituted once it becomes part of structure A.

[0317] C. OLEDs and Devices of the Present Disclosure In another aspect, the present disclosure also provides an OLED device comprising a first organic layer comprising a compound disclosed in the above Compounds section of this disclosure.

[0318] In some embodiments, an OLED comprises an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises a first ligand L comprising a structure of Formula I described herein. A The compound includes compounds having the formula:

[0319] In some embodiments, the organic layer is selected from the group consisting of a HIL, a HTL, an EBL, an EML, a HBL, an ETL, and an EIL. In some embodiments, the organic layer can be an emissive layer, and the compounds described herein can be an emissive or non-emissive dopant.

[0320] In some embodiments, the organic layer can further comprise a host, and the host can be selected from the group consisting of triphenylene, carbazole, indolocarbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, 5λ 2 -benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, 5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene, azaborinine, oxaborinin, dihydroacridine, xanthene, dihydrobenzoazasiline, dibenzoxasiline, phenoxazine, phenoxathiin, phenothiazine, dihydrophenazine, fluorene, naphthalene, anthracene, phenanthrene, phenanthroline, benzoquinoline, quinoline, isoquinoline, quinazoline, pyrimidine, pyrazine, pyridine, triazine, boryl, silyl, aza-triphenylene, aza-carbazole, aza-indolocarbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, aza-5λ 2 -comprises at least one chemical group selected from the group consisting of benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, and aza-(5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene).

[0321] In some embodiments, the host may be selected from the group consisting of the following Host Group 1 structures: [ka] [ka] [ka] [ka] [ka] (In the formula, Each of J1 to J6 is independently C or N; L' is a direct bond or an organic linker; Each Y AA , Y BB , Y CC and Y DD are independently selected from the group consisting of no bond, a direct bond, O, S, Se, CRR', SiRR', GeRR', NR, BR, and BRR'; R A’ , R B’ , R C’ , R D’ , R E’ , R F’ , and R G’ each independently represents one to maximum substitution, or no substitution; 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 the general substituents defined herein; any two substituents can be joined or fused to form a ring; and where possible, each unsubstituted aromatic carbon atom can be replaced with one or more N to form an aza-substituted ring).

[0322] In some embodiments, L' is an organic linker 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', GeRR', alkylene, cycloalkyl, aryl, cycloalkylene, arylene, heteroarylene, and combinations thereof.

[0323] In some embodiments, at least one of J1-J3 is N. In some embodiments, at least two of J1-J3 are N. In some embodiments, all three of J1-J3 are N. In some embodiments, each Y CC and Y DDare independently O, S, or SiRR', or more preferably O or S. In some embodiments, at least one unsubstituted aromatic carbon atom is replaced with N to form an azacycle.

[0324] In some embodiments, the host is selected from the group consisting of EG1-MG1-EG1 through EG53-MG27-EG53, having the formula EGa-MGb-EGc, or EG1-EG1 through 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 through EG53 are shown below: [ka] The structures of MG1 to MG27 are shown below: [ka] In the MGb structure shown above, the two binding positions in the asymmetric structures MG10, MG11, MG12, MG13, MG14, MG17, MG24, and MG25 are labeled with numbers for identification purposes.

[0325] In some embodiments, the host may be any of its aza-substituted variants, 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 through h112 defined in the Host Group 2 list below, where MGb, EGa, and EGc are each defined as follows: [ka] In the above table, EGa and EGc structures bound to one of the asymmetric structures MG10, MG11, MG12, MG13, MG14, MG17, MG24, and MG25 are indicated with a numeric prefix that identifies their binding position in the MGb structure.

[0326] In some embodiments, the organic layer may further comprise a host, wherein the host comprises a metal complex.

[0327] In some embodiments, the light-emitting layer can include 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 can form an exciplex. In some embodiments, the light-emitting layer can include a third host. In some embodiments, the third host is selected from the group consisting of insulating hosts (wide bandgap hosts), hole-transporting hosts, and electron-transporting hosts. 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 light-emitting layer can include 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 electron-transporting host has a LUMO of 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 hole-transporting host has a HOMO of greater than -5.6 eV, greater than -5.5 eV, greater than -5.4 eV, or greater than -5.35 eV. The HOMO and LUMO values ​​can be determined using solution electrochemistry. Solution cyclic voltammetry and differential pulse voltammetry can be performed using a CH Instruments Model 6201B potentiostat with anhydrous dimethylformamide (DMF) solvent and tetrabutylammonium hexafluorophosphate as the supporting electrolyte. Glassy carbon, platinum wire, and silver wire were used as the working, counter, and reference electrodes, respectively.The electrochemical potential was determined by measuring the peak potential difference from differential pulse voltammetry for the internal ferrocene-ferrocenium redox couple (Fc / Fc). + ) can be referenced to the literature ((a) Fink, R.; Heischkel, Y.; Thelakkat, M.; Schmidt, H.-W. Chem. Mater. 1998, 10, 3620-3625; (b) Pommerehne, J.; Vestweber, H.; Guss, W.; Mahrt, RF; Bassler, H.; Porsch, M.; Daub, J. Adv. Mater. 1995, 7, 551). By referencing the cation and anion redox potentials to ferrocene (4.8 eV vs. vacuum), the corresponding highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energies can be determined.

[0328] In some embodiments, the compounds described herein may be sensitizers or components of sensitizers, and the device may further include an acceptor that accepts energy from the sensitizer. In some embodiments, the acceptor is the emitter in the device. In some embodiments, the acceptor may be a fluorescent material. In some embodiments, the compounds described herein may be used as phosphorescent sensitizers in OLEDs where one or more layers in the OLED include an acceptor in the form of one or more non-delayed fluorescent and / or delayed fluorescent materials. In some embodiments, the compounds described herein may be used as one component of an exciplex to be used as a sensitizer. As a phosphorescent sensitizer, the compound must be capable of energy transfer to the acceptor, which will either emit energy or further transfer energy to the final emitter. The concentration of the acceptor may range from 0.001% to 99.9%. The acceptor may be present either 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 fluorescent (TADF) material. In some embodiments, the acceptor is a non-delayed fluorescent material. In some embodiments, emission can come from any or all of the sensitizer, the acceptor, and the final emitter. In some embodiments, the acceptor has room temperature emission with a full width at half maximum (FWHM) of 50 nm, 45 nm, 40 nm, 35 nm, 30 nm, 25 nm, 20 nm, 15 nm, 10 nm, or 5 nm or less. A narrower FWHM means better color purity for OLED display applications.

[0329] As used herein, phosphorescence generally refers to the emission of photons accompanied by a change in electron spin quantum number. That is, the initial and final states of emission have different electron spin quantum numbers, such as from the T1 to the S0 state. Most Ir and Pt complexes currently used in OLEDs are phosphorescent emitters. In some embodiments, when exciplex formation involves triplet emitters, such exciplexes can also phosphoresce. On the other hand, fluorescent emitters generally refer to the emission of photons without a change in electron spin quantum number, such as from the S1 to the S0 state or from the D1 to the D0 state. Fluorescent emitters can be delayed fluorescent emitters or non-delayed fluorescent emitters. Depending on the spin state, fluorescent emitters can be singlet, doublet, or other multiplet emitters. It is believed that delayed fluorescence can increase the internal quantum efficiency (IQE) of fluorescent OLEDs beyond the 25% spin statistical limit. There are two types of delayed fluorescence: P-type delayed fluorescence and E-type delayed fluorescence. P-type delayed fluorescence arises from 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 state and the singlet excited state. Thermal energy can activate the transition from the triplet state back to the singlet state. This type of delayed fluorescence is also known as TADF. E-type delayed fluorescence properties can be found in exciplex systems or single compounds. Without being bound by theory, TADF emission is characterized by a small singlet-triplet energy gap (ΔE ) of 400 meV, 350 meV, 300 meV, 250 meV, 200 meV, 150 meV, 100 meV, or 50 meV or less. S-T) is believed to require a compound or exciplex. There are two main types of TADF emitters: donor-acceptor TADF and multi-resonance (MR) TADF. Single-component donor-acceptor TADF compounds are often constructed by connecting an electron donor moiety, such as an amino derivative or carbazole derivative, with 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 transport compound and an electron transport compound. Examples of MR-TADF materials include highly conjugated fused ring systems. In some embodiments, MR-TADF materials contain boron, carbon, and nitrogen atoms. Such materials may also contain other atoms, such as oxygen. In some embodiments, the reverse intersystem crossing time (T1 to S1) of delayed fluorescence emission at 293 K is 10 microseconds or less. In some embodiments, such a time can be greater than 10 microseconds and less than 100 microseconds.

[0330] In some embodiments, the OLED may include additional compounds selected from the group consisting of non-delayed fluorescent materials, delayed fluorescent materials, phosphorescent materials, and combinations thereof.

[0331] In some embodiments, the compounds of the invention described herein are phosphorescent materials.

[0332] 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 energy of the phosphorescent material transfers its excited state to another material within the OLED. In some embodiments, the phosphorescent material participates in charge transport within the OLED. In some embodiments, the phosphorescent material is a sensitizer or a component of a sensitizer, and the OLED further includes an acceptor. In some embodiments, the phosphorescent material forms an exciplex with another material within the OLED, e.g., a host material, an emitter material.

[0333] In some embodiments, the non-delayed fluorescent material or delayed fluorescent material is an emitter that emits light in an OLED. In some embodiments, the non-delayed fluorescent material or delayed fluorescent material does not emit light in an OLED. In some embodiments, the energy of the non-delayed fluorescent material or delayed fluorescent material transfers its excited state to another material in the OLED. In some embodiments, the non-delayed fluorescent material or delayed fluorescent material participates in charge transport in an OLED. In some embodiments, the non-delayed fluorescent material or delayed fluorescent material is an acceptor, and the OLED further comprises a sensitizer.

[0334] In some embodiments of the OLED, the delayed fluorescent material comprises at least one donor group and at least one acceptor group. In some embodiments, the delayed fluorescent material is a metal complex. In some embodiments, the delayed fluorescent material is a non-metal complex. In some embodiments, the delayed fluorescent material is a Pt, Pd, Zn, Cu, Ag, or Au complex (some of which are also called metal-assisted (MA) TADF). In some embodiments, the metal-assisted delayed fluorescent material comprises a metal-carbene bond. In some embodiments, the non-delayed fluorescent material or delayed fluorescent material is an 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-boranaphtho[3,2,1-de]anthracene, 5λ 2 ,9λ 2 -diaza-13b-boranaphtho[2,3,4-de]anthracene, 5-oxa-9λ 2In some embodiments, the non-delayed fluorescent material or the delayed fluorescent material comprises at least one chemical group selected from the group consisting of -aza-13b-boranaphtho[3,2,1-de]anthracene, azaborinine, oxaboriinine, dihydroacridine, xanthene, dihydrobenzoazasiline, dibenzoxasiline, phenoxazine, phenoxathiin, phenothiazine, dihydrophenazine, fluorene, naphthalene, anthracene, phenanthrene, phenanthroline, benzoquinoline, quinoline, isoquinoline, quinazoline, pyrimidine, pyrazine, pyridine, triazine, boryl, amino, silyl, aza-variants thereof, and combinations thereof. In some embodiments, the non-delayed fluorescent material or the delayed fluorescent material comprises a tri(aryl / heteroaryl)borane in which one or more pairs of aryl / heteroaryl-derived substituents are bonded to form a ring. In some embodiments, the fluorescent material comprises at least one chemical group selected from the group consisting of naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene.

[0335] In yet another aspect, the OLED of the present disclosure may also include a light-emitting region comprising a compound or a combination of compounds disclosed in the above Compounds section of this disclosure. In some embodiments, the light-emitting region comprises a first ligand L having a structure of Formula I described herein. Aor a blend of compounds thereof. In some embodiments, the light-emitting region is comprised 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 Å, 400 Å, 450 Å, 500 Å, 550 Å, 600 Å, 650 Å, and 700 Å. In some embodiments, at least one of the one or more organic layers is formed from a light-emitting system having a figure of merit (FOM) value equal to or greater than a number 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. A definition of FOM is available in U.S. Patent Application Publication No. 2023 / 0292605, the entire contents of which are incorporated herein by reference. In some embodiments, at least one of the one or more organic layers comprises a compound or a combination of compounds disclosed in Sections A and D of this disclosure.

[0336] In some embodiments, an OLED or light-emitting region comprising a compound of the present invention disclosed herein can be incorporated into a full-color pixel array of a device. The full-color pixel array of such a device includes at least one pixel, where the at least one pixel comprises a first subpixel and a second subpixel. The first subpixel comprises a first OLED comprising a first light-emitting region. The second subpixel comprises a second OLED comprising a second light-emitting region. In some embodiments, the first and / or second OLEDs, first and / or second light-emitting regions, can be the same or different, and each can independently have various device characteristics and various embodiments of the compounds of the present invention contained therein, as well as various combinations and subcombinations of various device characteristics and various embodiments of the compounds of the present invention contained therein, as disclosed herein.

[0337] In some embodiments, the first light-emitting region has a peak wavelength λ max1 and the second light-emitting region is configured to emit light having a peak wavelength λ max2In some embodiments, the light source is configured to emit light having a peak wavelength λ max1 and λ max2 The difference between the peak wavelengths λ and λ is at least 4 nm, but within the same color range, such as the light blue and dark blue light described above. In some embodiments, the first light-emitting region has a peak wavelength λ in one of the regions of the visible spectrum: 400 to 500 nm, 500 to 600 nm, or 600 to 700 nm. max1 and the second light-emitting region is configured to emit light having a peak wavelength λ in one of the remaining regions of the visible spectrum: 400-500 nm, 500-600 nm, 600-700 nm. max2 In some embodiments, the first light-emitting region includes a first number of light-emitting layers, if greater than one, stacked on top of one another, and the second light-emitting region includes a second number of light-emitting layers, if greater than one, stacked on top of one another, the first number being different from the second number. In some embodiments, both the first and second light-emitting regions include phosphorescent materials, which may be the same or different. In some embodiments, the first light-emitting region includes a phosphorescent material and the second light-emitting region includes a fluorescent material. In some embodiments, both the first and second light-emitting regions include fluorescent materials, which may be the same or different.

[0338] In some embodiments, at least one pixel of an OLED or emissive region includes a total of N subpixels, the N subpixels including the first subpixel and the second subpixel, each of the N subpixels including an emissive region, and the total number of emissive regions in the at least one pixel is N-1 or less. In some embodiments, the second emissive region is identical to the first emissive region, and each subpixel of the at least one pixel includes one emissive region that is identical to the first emissive region. In some embodiments, the full-color pixel array may have a plurality of pixels including a first pixel region and a second pixel region, wherein at least one display characteristic in the first pixel region differs from a corresponding display characteristic in the second pixel region, and the at least one display characteristic is selected from the group consisting of resolution, cavity mode, color, outcoupling, and color filter.

[0339] In some embodiments, the OLED is a stacked OLED including one or more charge generating layers (CGLs). In some embodiments, the OLED includes a first electrode, a first light-emitting region disposed on the first electrode, a first CGL disposed on the first light-emitting region, a second light-emitting region disposed on the first CGL, and a second electrode disposed on the second light-emitting region. In some embodiments, the first and / or second light-emitting regions can have various device characteristics as described above for the pixelated device. In some embodiments, the stacked OLED is configured to emit white light. In some embodiments, one or more light-emitting regions in a pixelated OLED or stacked OLED include a sensitizer and an acceptor having various sensitizing device characteristics and various embodiments of the compounds of the present invention disclosed herein. For example, the first light-emitting region is included in a sensitized device and the second light-emitting region is not included in a sensitized device; in some examples, both the first and second light-emitting regions are included in a sensitized device.

[0340] In some embodiments, the OLED can emit at least 1%, 5%, 10%, 30%, 50%, 70%, 80%, 90%, 95%, 99%, or 100% of its light from a plasmonic mode. In some embodiments, at least one of the anode, cathode, or an additional layer disposed on the organic light-emitting layer functions as an enhancement layer. The enhancement layer includes a plasmonic material that nonradiatively couples to the emitter material and exhibits a surface plasmon resonance that transfers excited-state energy from the emitter material to a nonradiative mode of surface plasmon polaritons. In some embodiments, the enhancement layer is located within a threshold distance from the organic light-emitting layer, and the emitter material has a total nonradiative decay rate constant and a total radiative decay rate constant due to the presence of the enhancement layer. At the threshold distance, the total nonradiative decay rate constant is equal to the total radiative decay rate constant. Another threshold distance is the distance at which the total radioactive decay rate constant divided by the sum of the total non-radiative and radioactive decay rate constants equals the photoluminescence yield of the luminescent material in the absence of the enhancement layer.

[0341] In some embodiments, the OLED further includes an outcoupling layer. In some embodiments, the outcoupling layer is disposed on the enhancement layer opposite the organic light-emitting layer. The outcoupling layer scatters energy from the surface plasmon polaritons. In some embodiments, this energy is scattered into free space as photons. In other embodiments, the energy is scattered from the surface plasmon mode into other modes of the device, such as, but not limited to, an organic waveguide mode, a substrate mode, or another waveguide mode. In some embodiments, one or more intervening layers can be disposed between the enhancement layer and the outcoupling layer. Examples of intervening layers can be dielectric materials, including organic, inorganic, perovskite, and oxides, and can include stacks and / or mixtures of these materials.

[0342] The enhancement layer alters the effective properties of the medium in which the emitter material resides, resulting in any or all of the following: a reduction in the emission rate; a change in the emission line shape; a change in the emission intensity with angle; a change in the stability of the emitter material; a change in the efficiency of the OLED; and a reduction in the efficiency roll-off of the OLED device. Placing an enhancement layer on the cathode side, the anode side, or both, or placing an enhancement layer itself as a CGL, results in an OLED device that utilizes any of the above effects. In addition to the specific functional layers shown in the various OLED examples described and illustrated herein, OLEDs according to the present disclosure can include any of the other functional layers frequently found in OLEDs.

[0343] In some embodiments, the enhancement layer can be composed of 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 can include at least one of 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 periodically, quasi-periodically, or randomly arranged wavelength-sized features, or periodically, quasi-periodically, or randomly arranged subwavelength-sized features.

[0344] In some embodiments, the outcoupling layer has periodically, quasi-periodically, or randomly arranged wavelength-sized features or periodically, quasi-periodically, or randomly arranged subwavelength-sized features. In some embodiments, the outcoupling layer can be composed of nanoparticles. In some embodiments, the outcoupling layer is composed of nanoparticles arranged on a material. In these embodiments, the outcoupling layer can be tunable by at least one of changing the size of the nanoparticles, changing the shape of the nanoparticles, changing the material of the nanoparticles, adjusting the thickness of the material, changing the refractive index of the material, adding an additional layer on the nanoparticles, changing the thickness of an enhancement layer, or changing the material of an enhancement layer. The nanoparticles of the device can be formed from at least one of a metal, a dielectric material, a semiconductor material, an alloy of metals, a mixture of dielectric materials, a 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 outcoupling layer is composed of at least metal nanoparticles, the metal being 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 outcoupling layer is formed by lithography.

[0345] In some embodiments of plasmonic devices, the emitter and / or host compound used in the light-emitting layer has a vertical dipole ratio (VDR) of 0.33 or greater, and in some such embodiments, the emitter and / or host compound has a VDR of 0.40, 0.50, 0.60, 0.70, or greater.

[0346] In yet another aspect, the present disclosure also provides a consumer product comprising an organic light emitting device (OLED) having an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer can comprise a compound or a blend of compounds disclosed in the Compounds section of this disclosure above.

[0347] 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 comprises a first ligand L comprising a structure of Formula I described herein. A The compound may include a compound having the formula:

[0348] Generally, an OLED comprises 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(s). The injected holes and electrons each migrate toward the oppositely charged electrode. When an electron and hole localize on the same molecule, an "exciton," a localized electron-hole pair with an excited energy state, is formed. Light is emitted via a photoemissive mechanism when the exciton relaxes. In some cases, the exciton may localize as an excimer or exciplex. Non-radiative mechanisms, such as thermal relaxation, can also occur but are generally considered undesirable.

[0349] FIG. 1 shows an organic light-emitting device 100. The drawing is not necessarily drawn to scale. Device 100 may include a substrate 110, an anode 115, a hole-injection layer (HIL) 120, a hole-transport layer (HTL) 125, an electron-blocking layer (EBL) 130, an emissive 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 compound cathode having a first conductive layer 162 and a second conductive layer 164. Device 100 may be fabricated by depositing the layers described, in order. The properties and functions of these various layers, as well as example materials, are described in further detail in U.S. Pat. No. 7,279,704, columns 6-10, which are incorporated by reference.

[0350] Further examples are available for each of these layers. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. Patent No. 5,844,363, which is incorporated by reference in its entirety. An example of a p-doped hole-transporting 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 by reference in its entirety. Examples of emissive and host materials are disclosed in U.S. Patent No. 6,303,238 to Thompson et al., which is incorporated by reference in its entirety. An example of an n-doped electron-transporting 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 by reference in its entirety. U.S. Patent Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entireties, disclose examples of cathodes, including composite cathodes with 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 by reference in their entireties. Examples of injection layers are provided in U.S. Patent Application Publication No. 2004 / 0174116, which is incorporated by reference in its entirety. A description of protective layers can be found in U.S. Patent Application Publication No. 2004 / 0174116, which is incorporated by reference in its entirety.

[0351] FIG. 2 shows 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 described, in order. Because the most common OLED configuration has the cathode disposed above the anode, and device 200 has cathode 215 disposed below anode 230, device 200 can be referred to as an "inverted" OLED. Materials similar to those described with respect to device 100 may be used in the corresponding layers of device 200. FIG. 2 provides an example of how some layers can be omitted from the structure of device 100.

[0352] The simple layer structures illustrated in Figures 1 and 2 are provided as non-limiting examples, and it is understood that embodiments of the present disclosure can be used in conjunction with a wide variety of other structures. The specific materials and structures described are exemplary in nature, and other materials and structures may be used. A functional OLED may be achieved by combining the various layers described in various ways, or layers may be omitted entirely based on design, performance, and cost factors. Other layers not specifically described may also be included. Materials other than those specifically described may be used. While many of the examples provided herein describe various layers as including a single material, it is understood that combinations of materials, such as mixtures of hosts and dopants, or more generally, mixtures, may be used. Layers may also have various sublayers. The names given to the various layers herein are not intended to be strictly limiting. For example, in device 200, hole-transport layer 225 transports holes and injects holes into emissive layer 220 and may be described as a hole-transport layer or a hole-injection layer. In one embodiment, an OLED may be described as having an "organic layer" disposed between a cathode and an anode. The organic layer may include a single layer or may further include multiple layers of different organic materials, for example, as described with respect to Figures 1 and 2.

[0353] Structures and materials not specifically described may also be used, such as OLEDs (PLEDs) composed of polymeric materials, such as those disclosed in U.S. Pat. No. 5,247,190 to Friend et al., which is incorporated by reference in its entirety. As a further example, an OLED having a single organic layer may be used. OLEDs may be stacked, for example, as described in U.S. Pat. No. 5,707,745 to Forrest et al., which is incorporated by reference in its entirety. OLED structures may deviate from the simple layered structures illustrated in FIGS. 1 and 2. For example, the substrate may include angled reflective surfaces to improve outcoupling, such as the mesa structure described in U.S. Pat. No. 6,091,195 to Forrest et al. and / or the recessed structure described in U.S. Pat. No. 5,834,893 to Bulovic et al., which are incorporated by reference in their entirety.

[0354] Unless otherwise specified, any of the layers of the various embodiments can be deposited by any suitable method. For organic layers, preferred methods include deposition by thermal evaporation, such as those described in U.S. Pat. Nos. 6,013,982 and 6,087,196, which are incorporated by reference in their entirety; inkjet deposition; organic vapor phase deposition (OVPD), such as that described in U.S. Pat. No. 6,337,102 to Forrest et al., which is incorporated by reference in its entirety; and organic vapor jet printing (OVJP, also referred to as organic vapor jet deposition (OVJD)), such as that 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 performed in a nitrogen or inert atmosphere. For other layers, preferred methods include thermal evaporation, sputtering, chemical vapor deposition, atomic layer deposition, and electron beam evaporation. Preferred patterning methods include deposition via masks, photolithography, and cold welding, such as those described in U.S. Pat. Nos. 6,294,398 and 6,468,819, which are incorporated by reference in their entireties, as well as patterning associated with some deposition methods, such as inkjet and organic vapor jet printing (OVJP). Other methods may also be used. The material to be deposited may be modified to be compatible with a particular deposition method. For example, substituents such as alkyl and aryl groups, branched or unbranched, preferably containing at least three carbons, may be used in small molecules to enhance their ability to undergo solution processing. Substituents with 20 or more carbons may be used, with 3 to 20 carbons being a preferred range. Materials with asymmetric structures may have better solution processability than those with symmetric structures, because asymmetric materials may be less prone to recrystallization. Dendrimer substituents may be used to enhance the ability of small molecules to undergo solution processing.

[0355] Devices fabricated according to embodiments of the present disclosure may optionally further include a barrier layer. One purpose of the barrier layer is to protect the electrodes and organic layers from damaging exposure to harmful species in the environment, including moisture, vapors, and / or gases. The barrier layer may be deposited on, under, or adjacent to the substrate, the electrode, or any other portion 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 or organic compounds, or both. Preferred barrier layers include multiple alternating layers of polymeric and non-polymeric materials; organic and inorganic materials; or mixtures of polymeric and non-polymeric materials, examples of which are described in U.S. Pat. No. 7,968,146, PCT Patent Application Nos. PCT / US2007 / 023098 and PCT / US2009 / 042829, which are incorporated herein by reference in their entireties.

[0356] Devices made according to embodiments of the present disclosure can be incorporated into a wide variety of electronic component modules (or units) that can be incorporated into various electrical products or intermediate components. Examples of such electrical 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. Such electronic component modules can optionally include drive electronics and / or power sources. Devices made according to embodiments of the present disclosure can be incorporated into a wide variety of consumer products having one or more integrated electronic component modules (or units). Consumer products are disclosed that include OLEDs that include compounds of the present disclosure in the organic layer of the OLED. Such consumer products include any type of product that includes one or more light sources and / or one or more visual displays of some kind. Some examples of such consumer products include flat panel displays, curved displays, computer monitors, medical monitors, televisions, billboards, lights for indoor or outdoor illumination and / or signaling, head-up displays, fully or partially transparent displays, flexible displays, rollable displays, foldable displays, stretchable displays, laser printers, telephones, mobile phones, tablets, phablets, personal digital assistants (PDAs), wearable devices, laptop computers, digital cameras, camcorders, viewfinders, microdisplays (displays less than 2 inches diagonal), 3-D displays, virtual reality or augmented reality displays, vehicles, video walls including multiple displays aligned together, theater or stadium screens, phototherapy devices, and signage. A variety of control mechanisms, including passive matrix and active matrix, can be used to control devices made according to the present disclosure. Many of the devices are intended for use within a temperature range comfortable to humans, such as 18°C ​​to 30°C, and more preferably room temperature (20-25°C), but can also be used outside this temperature range, e.g., between -40°C and +80°C.

[0357] Further details regarding OLEDs and the definitions set forth above can be found in US Pat. No. 7,279,704, which is incorporated by reference in its entirety.

[0358] The materials and structures described herein may have applications in devices other than OLEDs. For example, other optoelectronic devices, such as organic solar cells and organic photodetectors, may use the materials and structures. More generally, organic devices, such as organic transistors, may use the materials and structures.

[0359] In some embodiments, the OLED has one or more properties selected from the group consisting of flexibility, rollability, foldability, stretchability, and bendability. In some embodiments, the OLED is transparent or translucent. In some embodiments, the OLED further comprises a layer comprising carbon nanotubes. In some embodiments, the OLED further comprises one or more quantum dots. Such quantum dots may be present in the emissive layer or other functional layers, such as a down-conversion layer.

[0360] In some embodiments, the OLED comprises an RGB pixel array or a white and color filter pixel array. 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 having a diagonal of less than 10 inches or an area of ​​less than 50 square inches. In some embodiments, the OLED is a display panel having a diagonal of at least 10 inches or an area of ​​at least 50 square inches. In some embodiments, the OLED is a lighting panel.

[0361] D. Other materials used in OLEDs The materials described herein are useful for specific layers in OLEDs in various examples. They 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 themselves in the EML or in conjunction 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 referenced below are non-limiting examples of materials that may be useful in combination with the compounds and devices disclosed herein; one of skill in the art can readily consult the literature to identify other materials that may be useful in combination.

[0362] a) Conductive (electrically conductive) dopants: The charge transport layer is doped with a conductive dopant to significantly alter the charge carrier density and thereby its conductivity. The 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 comprises at least one chemical moiety selected from the group consisting of cyano, fluorinated aryl or heteroaryl, fluorinated alkyl or cycloalkyl, alkylene, heteroaryl, amide, benzodithiophene, and highly conjugated heteroaryl groups extended with acyclic double bonds.

[0363] b) HIL / HTL: The hole injection / transport material used in the present disclosure is not particularly limited, and any compound may be used as long as the compound is typically used as a hole injection / transport material. Examples of such materials include phthalocyanine or porphyrin derivatives, aromatic amine derivatives, indolocarbazole derivatives, polymers containing fluorocarbons, polymers with conductive dopants, conductive polymers such as PEDOT / PSS, self-assembly monomers derived from compounds such as phosphonic acid and silane derivatives, and MoO. xp-type semiconducting organic compounds such as 1,4,5,8,9,12-hexaazatriphenylene hexacarbonitrile; metal complexes, and crosslinkable compounds.

[0364] Examples of aromatic amine derivatives used in HIL or HTL include those with the following general structure: [ka] These include, but are not limited to:

[0365] Ar 1 ~Ar 9each of which is a group consisting of aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene; 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, indole and aromatic heterocyclic compounds such as oxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and aromatic hydrocarbon cyclic groups and aromatic heterocyclic groups, which may be the same or different groups and which 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 cyclic group. 1 ~Ar 9 Each of may be unsubstituted or substituted with the generic substituents described above, and any two substituents may be joined or fused to form a ring.

[0366] In some embodiments, each Ar 1 ~Ar 9 is, independently, [ka] (wherein k is an integer of 1 to 20; X 101 ~X108 is C or N; Z 101 is C, N, O, or S).

[0367] Examples of metal complexes used in the HIL or HTL include those of the following general formula: [ka] (wherein Met is a metal that may have an atomic weight greater than 40; (Y 101 -Y 102 ) is a bidentate ligand, and Y 101 and Y 102 are independently selected from C, N, O, P, and S; 101 is another ligand; k' is an integer value from 1 to the maximum number of ligands that can be bound to the metal; and k' + k'' is the maximum number of ligands that can be bound to the metal).

[0368] In some embodiments, (Y 101 -Y 102 ) is a 2-phenylpyridine or 2-phenylimidazole derivative. In some embodiments, (Y 101 -Y 102 ) is a carbene ligand. In some embodiments, Met is selected from Ir, Pt, Pd, Os, Cu, and Zn. In some embodiments, the metal complex is + For the / Fc couple, it has a minimum oxidation potential of less than about 0.6 V in solution.

[0369] In some embodiments, the HIL / HTL materials include phthalocyanine and porphyrin compounds, starburst triarylamines, CF xThe conductive polymers are selected from the group consisting of fluorohydrocarbon polymers, conductive polymers (e.g., PEDOT:PSS, polyaniline, polythiophene), phosphonic acid and silane SAMs, triarylamine or polythiophene polymers with conductive dopants, organic compounds with conductive inorganic compounds (e.g., molybdenum and tungsten oxides), n-type semiconducting organic complexes, metal-organic complexes, crosslinkable compounds, polythiophene-based polymers and copolymers, triarylamines, triarylamines with spirofluorene cores, arylamine carbazole compounds, triarylamines with (di)benzothiophene / (di)benzofuran, indolocarbazoles, isoindole compounds, and metal carbene complexes.

[0370] c) EBL: An electron blocking layer (EBL) can be used to reduce the number of electrons and / or excitons that leave the emissive layer. The presence of such a blocking layer in a device can result in significantly higher efficiency and / or longer lifetime compared to a similar device lacking a blocking layer. A blocking layer can also be used to confine light emission to a desired region of an OLED. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and / or a higher triplet energy than 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 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 herein.

[0371] d) Host: 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 light emission of the dopant.

[0372] Examples of metal complexes that can be used as hosts include those having the general formula: [ka] (wherein Met is a metal; Y 103 -Y 104 ) is a bidentate ligand, and Y 103 and Y 104 are independently selected from C, N, O, P, and S; 101 is another ligand; k' is an integer value from 1 to the maximum number of ligands that can be bound to the metal; and k' + k'' is the maximum number of ligands that can be bound to the metal.

[0373] In some embodiments, the metal complex is [ka] where (ON) is a bidentate ligand with the metal coordinated to atoms O and N.

[0374] In some embodiments, Met is selected from Ir and Pt. 103 -Y 104 ) is a carbene ligand.

[0375] In some embodiments, the host compound is selected from the group consisting of the following: aromatic hydrocarbon ring compounds, such as benzene, biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene; aromatic heterocyclic compounds, such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazoline; 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 and at least one selected from the group consisting of benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, 5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene; and the group consisting of 2 to 10 cyclic structural units of the same or different types selected from aromatic hydrocarbon cyclic groups and aromatic heterocyclic groups, 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 cyclic group. Each option within each group may be unsubstituted, substituted by the common substituents described herein, or further fused.

[0376] In some embodiments, the host compound is [ka] (wherein k is an integer of 0 to 20 or 1 to 20. X 101 ~X 108 is independently selected from C or N. Z 101 and Z 102 is independently selected from C, N, O, or S).

[0377] In some embodiments, the host material is selected from the group consisting of arylcarbazoles, metal 8-hydroxyquinolates (e.g., alq3, balq), metal phenoxybenzothiazole compounds, conjugated oligomers and polymers (e.g., polyfluorenes), aromatic fused rings, zinc complexes, chrysene-based compounds, aryltriphenylene compounds, polyfused heteroaryl compounds, donor-acceptor type molecules, dibenzofuran / dibenzothiophene compounds, polymers (e.g., pvk), spirofluorene compounds, spirofluorene-carbazole compounds, indoloca The carbazoles, five-membered electron-deficient heterocycles (e.g., triazoles, oxadiazoles), tetraphenylene complexes, metal phenoxypyridine compounds, metal coordination complexes (e.g., Zn, Al with N^N ligands), dibenzothiophene / dibenzofuran-carbazole compounds, silicon / germanium aryl compounds, arylbenzoyl esters, carbazoles linked by non-conjugated groups, aza-carbazole / dibenzofuran / dibenzothiophene compounds, and high triplet metal organometallic complexes (e.g., metal-carbene complexes).

[0378] e) Emitter materials in the EML: One or more emitter materials can be used with the compounds or devices of the present disclosure. The emitter material can be emissive or non-emissive in the current device, as described herein. Examples of emitter materials are not particularly limited, and any compound can be used as long as it can generate light in a typical OLED device. Examples of suitable emitter materials include, but are not limited to, compounds that can generate light through 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 processes.

[0379] In some embodiments, the phosphor material is M(L 1 ) x (L 2 ) y (L 3 ) z has the formula: In the formula, L 1 , L 2 , and L 3 may be the same or different; x is 1, 2, or 3; y is 0, 1, or 2; z is 0, 1, or 2; x+y+z is the oxidation state of the metal M; L 1 is the structure of the ligand list: [ka] [ka] is selected from the group consisting of Each L 2 and L 3 is, independently, [ka] and the structures in the ligand list; M is selected from the group consisting of Ir, Rh, Re, Ru, Os, Pt, Pd, Zn, Au, Ag, and Cu; T is selected from the group consisting of B, Al, Ga, and In; K 1’ is a direct bond or NR e , PR e , O, S, and Se; Each Y 1 ~Y 15 is independently selected from the group consisting of carbon and nitrogen; Y' is BR e , N.R. e , PR e , O, S, Se, C=O, S=O, SO2, CR e R f , SiR e R f , and G e R e R f selected from the group consisting of: Each R a , R b , R c , and R d can independently represent one to the maximum possible number of substitutions, or no substitutions; 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 consisting of the general substituents defined herein; and Any two substituents can be fused or linked to form a ring or to form a multidentate ligand.

[0380] In some embodiments, the emitter material comprises a dopant from dopant group 1: [ka] [ka] [ka] is selected from the group consisting of where: X 96 ~X 99 each is independently C or N; Each Y 100 is independently selected from the group consisting of NR″, O, S, and Se; R 10a , R 20a , R 30a , R 40a , and R 50a each independently represents one substitution, up to one substitution, or no substitution; 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 of is independently hydrogen or a substituent selected from the group consisting of general substituents defined herein; any two substituents can be joined or fused to form a ring.

[0381] In some embodiments, the emitter material comprises a dopant from dopant group 2: [ka] [ka] [ka] [ka] [ka] [ka] is selected from the group consisting of where: Each Y 100 is independently selected from the group consisting of NR″, O, S, and Se; 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; X 100 and X 200 is, for each occurrence, selected from the group consisting of O, S, Se, NR'', and CR''R''''; Each R A’’ , R B’’ , R C’’ , R D’’ , R E’’ , and R F’’ independently represent mono-, up to, or no substitution; 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 of is independently hydrogen or a substituent selected from the group consisting of the general substituents defined herein; any two substituents can be joined or fused to form a ring.

[0382] In some embodiments of the above dopant groups 1 and 2, each unsubstituted aromatic carbon atom can be substituted with N to form an azacycle. 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, a Pt atom in each formula can be substituted with a Pd atom.

[0383] In some embodiments of the OLED, the delayed fluorescent material comprises at least one donor group and at least one acceptor group. In some embodiments, the delayed fluorescent material is a metal complex. In some embodiments, the delayed fluorescent material is a non-metal complex. In some embodiments, the delayed fluorescent material is a Zn, Cu, Ag, or Au complex.

[0384] In some embodiments of the OLED, the delayed fluorescent material is M(L 5 )(L 6 ) wherein M is Cu, Ag, or Au, and L 5 and L 6 is different and L 5 and L 6 is independently [ka] [ka] selected from the group consisting of: A 1 ~A 9 are each independently selected from C or N; Each R P , R Q , and R U independently represent mono-, up to, or no substitution; Each R P , R Q , R U , R SA , R SB , R RA , R RB , R RC , R RD , R RE , and R RFare independently hydrogen or a substituent selected from the group consisting of the general substituents defined herein; any two substituents can be joined or fused to form a ring.

[0385] In some embodiments of the OLED, the delayed fluorescent material is [ka] and at least one donor moiety selected from the group consisting of: where Y T , 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.

[0386] In some of the above embodiments, carbon ring atoms can be substituted with N, up to a total of three, along with their substituents, in each phenyl ring of any of the above structures.

[0387] In some embodiments, the delayed fluorescent material comprises at least one acceptor moiety selected from the group consisting of nitrile, isonitrile, borane, fluoride, pyridine, pyrimidine, pyrazine, triazine, azacarbazole, azadibenzothiophene, azadibenzofuran, azadibenzoselenophene, azatriphenylene, imidazole, pyrazole, oxazole, thiazole, isoxazole, isothiazole, triazole, thiadiazole, and oxadiazole. In some embodiments, the acceptor moiety and the donor moiety described herein are connected via a conjugated linker or sp 3 The connection can be direct through a non-conjugated linker such as a carbon or silicon atom.

[0388] In some embodiments, the fluorescent material is: [ka] [ka] comprising at least one chemical moiety selected from the group consisting of: where 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 SO; X F and X G are each independently selected from the group consisting of C and N.

[0389] In some of the above embodiments, carbon ring atoms can be substituted with N, up to a total of three, along with their substituents, in each phenyl ring of any of the above structures.

[0390] f) HBL: A hole-blocking layer (HBL) can be used to reduce the number of holes and / or excitons that escape from the emissive layer. The presence of such a blocking layer in a device can result in significantly higher efficiency and / or longer lifetime compared to a similar device lacking a blocking layer. A blocking layer can also be used to confine emission to a desired region of an OLED. In some embodiments, the HBL material has a lower HOMO (further away from the vacuum level) and / or a higher triplet energy than one or more of the emitters closest to the HBL interface.

[0391] In some embodiments, the compounds used in the HBL contain the same molecules or the same functional groups as those used as the hosts described above.

[0392] In some embodiments, the compound used in HBL is [ka] (wherein k is an integer of 1 to 20; L 101is another ligand, and k' is an integer from 1 to 3.

[0393] g)ETL: The electron transport layer (ETL) may include a material capable of transporting electrons. The electron transport layer may be intrinsic (undoped) or doped. Doping may be used to enhance conductivity. Examples of ETL materials are not particularly limited, and any metal complex or organic compound typically used to transport electrons may be used.

[0394] In some embodiments, the compounds used in the ETL have the following moiety in the molecule: [ka] and fullerene; wherein k is an integer from 1 to 20, and X 101 ~X 108 is selected from C or N; Z 101 is selected from the group consisting of C, N, O, and S.

[0395] In some embodiments, the metal complex used in the ETL has the following general formula: [ka] (wherein (ON) or (NN) is a bidentate ligand with a metal coordinated to atoms O, N, or N,N; L 101 is another ligand; and k' is an integer value from 1 to the maximum number of ligands that can be bound to the metal).

[0396] In some embodiments, the ETL material is selected from the group consisting of anthracene-benzimidazole compounds, azatriphenylene derivatives, anthracene-benzothiazole compounds, metal 8-hydroxyquinolates, metal hydroxybenzoquinolates, bathocuproine compounds, five-membered electron-deficient heterocycles (e.g., triazoles, oxadiazoles, imidazoles, benzimidazoles), silole compounds, arylborane compounds, fluorinated aromatic compounds, fullerenes (e.g., C60), triazine complexes, and Zn(N̂N) complexes.

[0397] h) Charge Generation Layer (CGL) In tandem or stacked OLEDs, the CGL plays a key role in performance and consists of an n-doped layer and a p-doped layer for electron and hole injection, respectively. Electrons and holes are supplied from the CGL and the electrodes. Consumed electrons and holes in the CGL are replenished by electrons and holes injected from the cathode and anode, respectively, until the bipolar current gradually reaches a steady state. Typical CGL materials contain n-type and p-type conductivity dopants used in the transport layers.

[0398] In any compound disclosed herein, hydrogen atoms can be partially or fully deuterated. The minimum amount of hydrogen in a deuterated compound is selected from the group consisting of 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 99%, and 100%. As used herein, percent deuteration has its usual meaning and includes the percentage of all possible hydrogen and deuterium atoms replaced by deuterium atoms. In some embodiments, deuterium atoms are bonded to aromatic rings. In some embodiments, deuterium atoms are bonded to saturated carbon atoms such as alkyl or cycloalkyl carbon atoms. In some other embodiments, deuterium atoms are bonded to heteroatoms such as Si or Ge atoms.

[0399] It is understood that the various embodiments described herein are by way of example only and are not intended to limit the scope of the invention. For example, many of the materials and structures described herein can be substituted with other materials and structures without departing from the spirit of the invention. Thus, the present invention as claimed may include variations from the specific examples and preferred embodiments described herein, as will be apparent to those skilled in the art. It is understood that various theories as to why the invention works are not intended to be limiting.

[0400] E. Experimental Section Material synthesis Synthesis of compound 3 [ka] 2-(3-methoxydibenzo[b,d]furan-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, 1 (10.0 g, 1 equiv., 30.85 mmol), 1-bromo-3-chloro-2-fluorobenzene, 2 (7.11 g, 1.1 equiv., 33.93 mmol), SPhos (2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl) (633.2 mg, 0.05 equiv., 1.542 mmol), and SPhos in acetonitrile (100 mL) To a mixture of Pd(crotyl)Cl ((1,2,3-η)-2-buten-1-yl)chloro[dicyclohexyl(2',6'-dimethoxy[1,1'-biphenyl]-2-yl)phosphine-κP]palladium) (962 mg, 0.05 equiv., 1.542 mmol) was added a solution of KCO (12.8 g, 3 equiv., 92.54 mmol) in water (25 mL). The mixture was degassed with nitrogen for 10 minutes and then heated to 65 °C overnight (approximately 12 hours). The mixture was diluted with water (200 mL), and the aqueous layer was extracted with ethyl acetate (EtOAc) (3 × 100 mL). The combined organic extracts were washed with brine (150 mL), dried over NaSO, filtered, and concentrated in vacuo. The crude product was purified by chromatography on silica gel to give 2-(3-chloro-2-fluorophenyl)-3-methoxydibenzo[b,d]furan, 3 (9.25 g, 27 mmol, 86%) as a white solid.

[0401] Synthesis of compound 4 [ka] To a solution of 2-(3-chloro-2-fluorophenyl)-3-methoxydibenzo[b,d]furan, 3 (9.25 g, 1 equiv., 26.61 mmol) in dry dichloromethane (DCM) (100 mL) at 0 °C was added dropwise a DCM solution of BBr3 (47.90 mL, 1.000 mol, 1.8 equiv., 47.90 mmol). The mixture was stirred at 0 °C for 1 h and then at 25 °C for 3 h. The mixture was placed in an ice bath and quenched by the slow addition of cold water (200 mL). The aqueous layer was extracted with DCM (3 × 200 mL). The combined organic extracts were washed with brine (200 mL), dried over NaSO, filtered, and concentrated in vacuo to give the desired product 2-(3-chloro-2-fluorophenyl)dibenzo[b,d]furan-3-ol, 4 (8.700 g, 26 mmol, 96%) as a light brown solid.

[0402] Synthesis of compound 5 [ka] To a solution of 3-(3-chloro-2-fluorophenyl)dibenzo[b,d]furan-2-ol, 4 (9.00 g, 1 equiv., 26.48 mmol) in ethanol (100 mL) was added NBS (N-bromosuccinimide) (4.95 g, 1.05 equiv., 27.80 mmol) at 0 °C. The resulting reaction mixture was stirred at 0 °C for 30 minutes and then at 25 °C for 3 hours. The mixture was diluted with water (200 mL), and the aqueous layer was extracted with ethyl acetate (EtOAc) (3 × 150 mL). The combined organic extracts were washed with brine (200 mL), dried over NaSO, filtered, and concentrated in vacuo. The crude product was purified by chromatography on silica gel to give 1-bromo-3-(3-chloro-2-fluorophenyl)dibenzo[b,d]furan-2-ol, 5 (10.0 g, 25 mmol, 95%) as a pale yellow solid.

[0403] Synthesis of compound 6 [ka] To a solution of 1-bromo-3-(3-chloro-2-fluorophenyl)dibenzo[b,d]furan-2-ol, 5 (10.0 g, 1 equiv., 25.02 mmol) in NMP (N-methyl-2-pyrrolidone) (200 mL), potassium carbonate (10.4 g, 3 equiv., 75.07 mmol) was added, and the reaction mixture was stirred at 100 °C overnight (approximately 12 h). The reaction mixture was cooled, and water (200 mL) was added slowly with stirring. The resulting solution was then allowed to stand for 30 min. The solution was filtered and washed several times with water to remove excess NMP. The white solid was taken up in a DCM / CHCl mixture (1:2), dried over NaSO, and concentrated to dryness under reduced pressure. The solid was triturated in MeOH for 2 h, then filtered and dried overnight under vacuum to give the pure desired product (6) as a white solid.

[0404] Synthesis of Compound 1 of the Present Invention [ka] Example 1 of the present invention can be synthesized according to the above scheme. Coupling reaction of 6 with 3,6-di-tert-butyl-9H-carbazole gives 7, which can be converted to 8 by Miyaura borylation followed by coupling with 2-chloro-4-(2,2-dimethylpropyl-1,1-d2)-5-(methyl-d3)pyridine. Ligation reaction of compound 8 with dimer 9 gives compound 1 of the present invention as the desired product.

[0405] Synthesis of Compound 4 of the Present Invention [ka] Example 4 of the present invention can be synthesized according to the above scheme. Coupling of 6 with [1,1'-biphenyl]-4-ylboronic acid gives 10, which can be converted to 11 by Miyaura boronation followed by coupling with 2-chloro-4-(2,2-dimethylpropyl-1,1-d2)-5-(methyl-d3)pyridine. Ligation of compound 11 with dimer 9 gives compound 4 of the present invention as the desired product.

[0406] Synthesis of Compound 7 of the Invention [ka] Example 7 of the present invention can be synthesized according to the above scheme. Coupling of 6 with 2-(3,5-diisopropyl-[1,1'-biphenyl]-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane gives 12, which can be converted to 13 by boronation followed by coupling with 2-chloro-4-(2,2-dimethylpropyl-1,1-d2)-5-(methyl-d3)pyridine. Ligation of 13 with dimer 9 gives compound 7 of the present invention as the desired product.

[0407] Synthesis of Compound 19 of the Invention [ka] Example 19 of the present invention can be synthesized according to the above scheme. Coupling of 6 with 2-(3,5-di-tert-butylphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane gives 14, which can be converted to 15 by Miyaura boronation followed by coupling with 2-chloro-4-(2,2-dimethylpropyl-1,1-d2)-5-(methyl-d3)pyridine. Ligation of compound 15 with dimer 9 gives compound 19 of the present invention as the desired product.

[0408] Synthesis of Compound 20 of the Invention [ka] Example 20 of the present invention can be synthesized according to the above scheme. Coupling of 6 with 2-([1,1':3',1''-terphenyl]-5'-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane gives 16, which can be converted to 17 by boronation followed by coupling with 2-chloro-4-(2,2-dimethylpropyl-1,1-d2)-5-(methyl-d3)pyridine. Ligation of compound 17 with dimer 9 gives compound 20 of the present invention as the desired product.

[0409] Synthesis of compound 19 [ka] 1-Bromo-4-iodo-2-methoxybenzene 18 (60.0 g, 1.0 equiv., 192 mmol) was dissolved in dry DCM (600 mL) under nitrogen and cooled to 0 °C. Dichloro(methoxy)methane (28.7 g, 22.5 mL, 1.3 equiv., 249 mmol) was then added portionwise over 2 min, followed by TiCl (1 M in DCM, 403 mL, 2.1 equiv., 403 mmol) portionwise over 40 min (maintaining the internal temperature below 5 °C). The reaction mixture was allowed to warm to room temperature with stirring overnight, cooled to 0 °C, and then quenched by the careful addition of 1 M aqueous HCl (500 mL) over 15 min. The layers were separated, and the aqueous layer was extracted with DCM (2 × 600 mL). The combined organic extracts were dried over Na SO , filtered, and concentrated in vacuo. The solid was then dried azeotropically with acetonitrile (MeCN) to give 67.2 g of a lavender solid. The lavender solid was suspended in MeCN (50 ml) and stirred at room temperature for 2 hours. The solid was filtered off and dried in vacuo to give 5-bromo-2-iodo-4-methoxybenzaldehyde 19 (83%, 59.3 g) as a pale gray solid.

[0410] Synthesis of compound 20 [ka] 5-Bromo-2-iodo-4-methoxybenzaldehyde 19 (50.3 g, 1.0 equiv., 143 mmol), 5-chloro-2-formylphenyl)boronic acid (29.0 g, 1.1 equiv., 157 mmol), and K2CO3 (75.2 g, 3.8 equiv., 544 mmol) were suspended in dry dimethyl sulfoxide (DMSO) (840 mL) and sparged with nitrogen for 25 minutes. PdCl2dppf.DCM (dichlorobis(triphenylphosphine)palladium(II) dichloromethane solvate) (11.7 g, 0.1 equiv., 14.3 mmol) was added, and the reaction mixture was heated to 80 °C for 2.5 hours. The reaction mixture was cooled to room temperature and then diluted with methyl tert-butyl ether (MtBE) (500 mL) and water (350 mL). The resulting biphasic mixture was passed through filter paper to remove interphase solids. The filtrate phases were separated, and the aqueous phase was extracted with MtBE (2 × 500 mL). The combined organics were washed with brine (2 × 300 mL), then dried over MgSO, filtered, and concentrated in vacuo to give a dark brown oil. The dark brown oil was purified by flash column chromatography, eluting with 0–30% (1:1 EtOAc:DCM) in hexanes. Pure fractions were combined and concentrated in vacuo to give 4-bromo-5′-chloro-5-methoxy-[1,1′-biphenyl]-2,2′-dicarbaldehyde 20 (37.0 g, 0.1 mol, 72%) as a pale yellow oily foam.

[0411] Synthesis of compound 21 [ka] 4-Bromo-5'-chloro-5-methoxy-[1,1'-biphenyl]-2,2'-dicarbaldehyde 20 (22.2 g, 1.0 equiv., 61.6 mmol) was dissolved in glacial acetic acid (AcOH) (420 mL) under nitrogen, and the mixture was heated to 100 °C. A solution of hydrazine hydrate (4.32 g, 4.23 mL, 1.4 equiv., 86.2 mmol) in glacial acetic acid (42 mL) (dissolved at 0 °C due to a strong exotherm) was added dropwise over 5 min, and the reaction mixture was stirred at 100 °C for 3 h. The reaction mixture was cooled to room temperature, transferred to a beaker in an ice bath, and carefully quenched with ice water (260 mL) over 10 min. Then, 2 M aqueous NaOH (650 mL) was slowly added over 10 min, and the resulting mixture was stirred at 10–15 °C for 15 min. The resulting solid was filtered off, washed with water (3 × 100 mL), transferred to a round-bottom flask (RBF) with DCM (300 mL), dried in vacuo, and then azeotropically dried with acetonitrile (MeCN) to give 2-bromo-6-chloro-3-methoxyphenanthrene 21 (22.2 g, 60 mmol, 98%) as a tan solid.

[0412] Synthesis of compound 22 [ka] 2-Bromo-6-chloro-3-methoxyphenanthrene 21 (32.8 g, 1.0 equiv., 89.8 mmol) and (2-fluoro-3-methoxyphenyl)boronic acid (18.3 g, 1.2 equiv., 108 mmol) were dissolved in dioxane (360 mL) under nitrogen. Next, a solution of NaCO (28.5 g, 3.0 equiv., 269 mmol) in water (60 mL) was added, and the reaction mixture was thoroughly sparged with nitrogen for 20 min. Pd(PPh) (5.19 g, 0.05 equiv., 4.49 mmol) was added, and the reaction mixture was heated at 80 °C overnight. The reaction mixture was cooled to room temperature, diluted with water (300 mL), and stirred for 5 min. This mixture was extracted with DCM (600 mL), and the phases were separated. The aqueous phase was further extracted with DCM (2 × 300 mL), and the combined organic phases were washed with water (300 mL) and then saturated brine (300 mL), then dried over NaSO, filtered, and concentrated in vacuo to give 45.1 g of a dark brown oily solid. This dark brown oily solid was suspended in MeCN (175 mL) and stirred overnight at room temperature. The solid was filtered off and dried in vacuo to give 6-chloro-2-(2-fluoro-3-methoxyphenyl)-3-methoxyphenanthrene 22 (24.3 g, 62 mmol, 69%) as an orange solid.

[0413] Synthesis of compound 23 [ka] 6-Chloro-2-(2-fluoro-3-methoxyphenyl)-3-methoxyphenanthrene 22 (24.3 g, 1.0 equiv., 62.3 mmol) was dissolved in dry DCM (350 mL) under nitrogen and cooled to 0 °C. BBr3 (1 M in DCM, 131 mL, 2.1 equiv., 131 mmol) was added dropwise over 10 min, and the reaction mixture was allowed to warm slowly to room temperature over 3 h. The reaction mixture was added portionwise to ice-cold MeOH (170 mL) over 15 min, and the resulting mixture was stirred for 30 min. The resulting thin suspension was concentrated in vacuo to give a brown solid, which was suspended in water (250 mL) and stirred overnight at room temperature. The solid was filtered off and washed with water (30 mL) followed by hexane (30 mL). The washed solid was dried in vacuo and then azeotroped with MeCN to give a gray-brown solid. The gray-brown solid was suspended in MeCN (130 mL) and stirred at room temperature for 2 h, then placed in an ice / water bath and stirred for 10 min. The solid was filtered off and dried in vacuo to give a first crop of 6-chloro-2-(2-fluoro-3-hydroxyphenyl)phenanthren-3-ol 23 (10.4 g, 29 mmol, 46%) as a pale gray solid.

[0414] Synthesis of compound 24 [ka] 6-Chloro-2-(2-fluoro-3-hydroxyphenyl)phenanthren-3-ol 23 (20.9 g, 1.0 equiv., 58.08 mmol) was dissolved in dry NMP (450 mL) under nitrogen, followed by the addition of KCO (28.1 g, 3.5 equiv., 203.3 mmol), and the reaction mixture was heated at 170 °C overnight. The reaction was further heated at 190 °C for 30 h and then cooled to room temperature. The reaction mixture was diluted with MtBE (250 mL) and water (1.2 L), and the phases were separated. The aqueous phase was extracted with MtBE (4 × 250 mL). The combined organics were washed with water (2 × 150 ml) and then brine (3 × 150 ml) before being dried over NaSO, filtered, and concentrated in vacuo to give 2-chlorophenanthro[3,2-b]benzofuran-11-ol 24 (78%, 16.7 g, 52.5 mmol) as a light tan solid.

[0415] Synthesis of Compound 23 of the Invention [ka] Example 23 of the present invention can be synthesized according to the above scheme. CN coupling reaction of 24 with 3,6-di-tert-butyl-9H-carbazole gives 25, which can be converted to 26 by treatment with triflic anhydride in the presence of triethylamine followed by Miyaura boronation. Suzuki coupling of 26 with 2-chloro-4-(2,2-dimethylpropyl-1,1-d2)-5-(methyl-d3)pyridine gives 27, which is then ligated with dimer 9 to give compound 23 of the present invention as the desired product.

[0416] Synthesis of Compound 24 of the Invention [ka] Example 24 of the present invention can be synthesized according to the above scheme. Suzuki coupling of 24 with 2-(3,5-diisopropyl-[1,1'-biphenyl]-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane gives 28, which can be converted to 29 by treatment with trifluoromethanesulfonic anhydride in the presence of triethylamine followed by Miyaura boronation. Suzuki coupling of 29 with 2-chloro-4-(2,2-dimethylpropyl-1,1-d2)-5-(methyl-d3)pyridine gives 30, which is then ligated with dimer 9 to give compound 24 of the present invention as the desired product.

[0417] Synthesis of Compound 25 of the Invention [ka] Example 25 of the present invention can be synthesized according to the above scheme. Suzuki coupling of 24 with 2-(3,5-di-tert-butylphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane gives 31, which can be converted to 32 by treatment with trifluoromethanesulfonic anhydride in the presence of triethylamine followed by Miyaura boronation. Suzuki coupling of 32 with 2-chloro-4-(2,2-dimethylpropyl-1,1-d2)-5-(methyl-d3)pyridine gives 33, which is then ligated with dimer 9 to give compound 25 of the present invention as the desired product.

[0418] Synthesis of Compound 26 of the Invention [ka] Example 26 of the present invention can be synthesized according to the above scheme. Suzuki coupling of 24 with 2-([1,1':3',1''-terphenyl]-5'-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane gives 34, which can be converted to 35 by treatment with trifluoromethanesulfonic anhydride in the presence of triethylamine followed by Miyaura boronation. Suzuki coupling of 35 with 2-chloro-4-(2,2-dimethylpropyl-1,1-d2)-5-(methyl-d3)pyridine gives 36, which is then ligated with dimer 9 to give compound 26 of the present invention as the desired product.

[0419] Compound characterization Various compounds of the present invention and comparative compounds were evaluated computationally. Calculations were performed using the B3LYP functional with the CEP-31G basis set. Geometry optimizations were performed in vacuo. Time-dependent density functional theory (TDDFT) was used to obtain excitation energies for these optimized structures. In the TDDFT calculations, a continuum solvent model was applied to simulate the tetrahydrofuran solvent. All calculations were performed using the Gaussian program. The computational results obtained using the DFT functionals and basis sets specified above are theoretical. Computational hybrid protocols, such as Gaussian16 used here with the B3LYP and CEP-31G protocols, are based on the assumption that electronic effects are additive and can therefore be extrapolated to the complete basis set (CBS) limit using larger basis sets. However, if the purpose of the study is to understand the variations in HOMO, LUMO, S1, T1, bond dissociation energies, etc. in a series of structurally related compounds, additive effects are expected to be similar. Therefore, although the absolute error when using B3LYP may be larger compared to other calculation methods, the relative differences in the HOMO, LUMO, S1, T1, and bond dissociation energy values ​​calculated with the B3LYP protocol are expected to reproduce experimental results very well. See, for example, Hong et al., Chem. Mater. 2016, 28, 5791–98, 5792–93, and the Supplementary Information (which discusses the reliability of DFT calculations in the context of OLED materials). Furthermore, for iridium and platinum complexes useful in OLED technology, data obtained from DFT calculations correlate very well with actual experimental data. See Tavasli et al., J. Mater. Chem. 2012, 22, 6419-29, 6422 (Table 3) (showing that DFT calculations for various luminescent complexes correlate closely with real data); Morello, GR, J. Mol. Model. 2017, 23:174 (studying various DFT functionals and basis sets and concluding that the combination of B3LYP and CEP-31G is particularly accurate for luminescent complexes). Determination of excited state transition properties is performed as a post-processing step of the above DFT and TDDFT calculations.This analysis allows the decomposition of excited states into the hole (i.e., where the excitation occurs) and the electron (i.e., the final location of the excited state). Furthermore, this analysis is objective and reproducible because it is based on calculated properties; see Mai et al., Coord. Chem. Rev. 2018, 361, 74-97 (which discusses the rationale for excited state decomposition in transition metal complexes).

[0420] VDR was calculated from the transition dipole moment (TDM) using density functional theory including spin-orbit coupling, and calculated as a weighted average of possible TDM orientations. The VDRs of Compounds 1 to 22 of the present invention are reported as relative values ​​normalized to the results of Comparative Compound 1; the VDR of Compound 23 of the present invention is reported as relative values ​​normalized to the results of Comparative Compound 2. The T1, S1, HOMO, LUMO, and VDR of selected compounds are shown in Table 1 below. [Table 1-1] [Table 1-2] [Table 1-3] [Table 1-4] [Table 1-5]

[0421] The calculated data in Table 1 show that the compounds of the present invention have lower VDR values ​​than the applicable comparative compounds. It is believed that the features of the present invention should enable the VDR value to be adjusted to a commercially desirable range. It is also believed that the EQE is directly related to the degree of orientation of the emitter compound. Within the same compound series, more highly oriented emitter compounds are expected to exhibit lower VDRs and higher EQEs. The compounds of the present invention exhibit relative VDR values ​​ranging from 0.526 to 0.816, which is believed to correlate with higher efficiencies than the comparative compounds in commercial OLED devices.

Claims

1. First Ligand L Ａ A compound having the formula: The first ligand L Ａ has the structure of Formula I: 【Chemistry 1】 (In the formula, Moieties A and D are each independently a monocyclic ring or a polycyclic fused ring system, and each ring of the monocyclic ring or polycyclic fused ring system is independently a 5- to 10-membered carbocyclic or heterocyclic ring; The moiety C is a 5- or 6-membered carbocyclic or heterocyclic ring; Z １ , Z ２ and X １ ~X ４ each is independently C or N; Part A is X １ ~X ４ and binds to one of the X １ ~X ４ one of which is C; Y is BR, BRR', NR, PR, P(O)R, O, S, Se, C=O, C=S, C=Se, C=NR', C=CRR', S=O, SO ２ , CR, CRR′, SiRR′, and GeRR′; K is 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 ) selected from the group consisting of; R Ａ , R Ｂ , R Ｃ , and R Ｄ each independently represents one to the maximum number of substitutions or no substitutions; Each R, R', R α , R β , R Ａ , R Ｂ , R Ｃ , and R Ｄ is independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boryl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, selenyl, and combinations thereof; At least one R Ｃ or R Ｄ is a substituent R containing a carbocyclic or heterocyclic group ＊ ) L Ａ is coordinated to the metal M; M is selected from the group consisting of Ir, Rh, Re, Ru, Os, Pt, Pd, Ag, Au, and Cu; M may be coordinated to other ligands; L Ａ may be combined with other ligands to comprise a tridentate, tetradentate, pentadentate, or hexadentate ligand; any two substituents may be joined or fused to form a ring; and Subject to the following conditions: (1) The moiety C is a six-membered ring and R Ｃ or R Ｄ is R ＊ If R ＊ is not an unsubstituted phenyl group or a phenyl group substituted with an electron-withdrawing group; (2) Moiety C and moiety D together form a naphthalene ring, and R Ｃ is R ＊ If R ＊ is not unsubstituted carbazole, 2,7-di-tert-butyl-carbazole, or 3,5-di-tert-butyl-carbazole; and (3) R Ｄ is R ＊ If R ＊ is a compound not selected from list RD as defined herein.

2. Each of moieties A and D is independently selected from the following list of cyclic moieties: benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole, triazole, cyclopentadiene, selenophene, naphthalene, quinoline, isoquinoline, quinazoline, benzofuran, aza-benzofuran, phenanthro[3,2-b]benzofuran, benzoxazole, aza-benzoxazole, benzothiophene, aza-benzothiophene, benzothiazole, aza-benzothiazole, benzoselenophene, aza-benzoselenophene, indole, benzoselenophene, benzoisopropyl ... and / or the moiety C is selected from the group consisting of phenylene, aza-indene, indole, aza-indole, benzimidazole, aza-benzimidazole, benzobenzimidazole, aza-benzobenzimidazole, carbazole, aza-carbazole, naphtho-imidazole, dibenzofuran, aza-dibenzofuran, dibenzothiophene, aza-dibenzothiophene, quinoxaline, phthalazine, phenanthrene, aza-phenanthrene, anthracene, aza-anthracene, phenanthridine, fluorene, and aza-fluorene; and / or the moiety C is a 6-membered ring; and / or the metal is Ir or Pt; and / or Z １ is N and Z ２ is C; and / or X １ ~X ４ Each of is C or X １ ~X ４ and / or Y is selected from the group consisting of CRR′, SiRR′, NR, O, S, and Se; and / or K is a direct bond, O, or S; and / or Z ２ is X １ binds to and / or At least one R Ａ includes a substituent selected from the group consisting of alkyl, cycloalkyl, silyl, germyl, aryl, heteroaryl, and combinations thereof; and / or at least one R Ｂ includes a substituent selected from the group consisting of alkyl, cycloalkyl, silyl, germyl, aryl, heteroaryl, and combinations thereof; and / or at least one R Ｃ includes a substituent selected from the group consisting of alkyl, cycloalkyl, silyl, germyl, aryl, heteroaryl, and combinations thereof; and / or at least one R Ｄ contains a substituent selected from the group consisting of alkyl, cycloalkyl, silyl, germyl, aryl, heteroaryl, and combinations thereof; and / or at least one of R or R′ contains a substituent selected from the group consisting of alkyl, cycloalkyl, silyl, germyl, aryl, heteroaryl, and combinations thereof; and / or the substituent R ＊ is the structure of List A below: 【Chemistry 2】 【Transformation 3】 【Chemistry 4】 【Transformation 5】 【Transformation 6】 【Transformation 7】 【Transformation 8】 【Chemistry 9】 【Chemistry 10】 【Chemistry 11】 【Chemistry 12】 【Chemistry 13】 【Chemistry 14】 【Chemistry 15】 【Chemistry 16】 10. The compound of claim 1, wherein the compound is selected from the group consisting of: wherein (D)H indicates that the moiety can be either H or D.

3. Ligand L Ａ But the following structure in Listing 1: 【Chemistry 17】 [Chemistry 18] 【Chemistry 19】 【Chemistry 20】 【Chemistry 21】 (In the formula, X １ ~X ６ and X ８ ~X １９ are each independently C or N; Y Ａ , Y Ｂ , and Y Ｃ Each of the groups independently represents BR ｅ , N.R. ｅ , P.R. ｅ , O, S, Se, C=O, S=O, SO ２ , C.R. ｅ R ｆ , SiR ｅ R ｆ , and GeR ｅ R ｆ selected from the group consisting of: Each R Ａ１ , R Ｂ１ , R Ｂ２ , and R Ｂ３ independently represent one to the maximum possible number of substitutions, or no substitutions; Each R Ａ１ , R Ｂ１ , R Ｂ２ , R Ｂ３ , R ｅ , and R ｆ are independently hydrogen or a substituent selected from the group consisting of the general substituents defined herein; any two substituents may be joined or fused to form a ring; and At least one R Ｂ２ or R Ｂ３ is a substituent R containing a carbocyclic or heterocyclic group ＊ 2. The compound of claim 1, wherein

4. Ligand L Ａ But, L Ａｉ (R Ｈ ) (R Ｉ ) (R Ｊ ) (R Ｋ ) (R Ｌ ), L Ａｉ’ (R Ｈ ) (R Ｉ ) (R Ｊ ) (R Ｋ’ ) (R Ｌ ), L Ａｉ’’ (R Ｈ ) (R Ｉ ) (R Ｊ ) (R Ｋ’’ ) (R Ｌ ), L Ａ’ｎ (R Ｈ ) (R Ｉ ) (R Ｊ ) (R Ｋ ) (R Ｌ ) and L Ａ’ｎ’ (R Ｈ ) (R Ｉ ) (R Ｊ ) (R Ｋ ) (R Ｋ’’ ) (R Ｌ ), where i is an integer from 1 to 11, i' is an integer from 12 to 37, i'' is an integer from 38 to 43, n is an integer from 1 to 12, and n' is an integer from 13 to 26; Ｈ , R Ｉ , R Ｊ , and R Ｋ are each independently selected from V1 to V192; R Ｌ is selected from O1 to O328; R Ｋ’ is selected from V1 to V180; R Ｋ’’ is selected from V1 to V178; and L Ａｉ (R Ｈ ) (R Ｉ ) (R Ｊ ) (R Ｋ ) (R Ｌ ), L Ａｉ’ (R Ｈ ) (R Ｉ ) (R Ｊ ) (R Ｋ’ ) (R Ｌ ), and L Ａｉ’’ (R Ｈ ) (R Ｉ ) (R Ｊ ) (R Ｋ’’ ) (R Ｌ ) are listed in List 3 below: 【Chemistry 22】 【Chemistry 23】 【Chemistry 24】 【Chemistry 25】 is defined in L Ａ’ｎ (R Ｈ ) (R Ｉ ) (R Ｊ ) (R Ｋ ) (R Ｌ ) and L Ａ’ｎ’ (R Ｈ ) (R Ｉ ) (R Ｊ ) (R Ｋ ) (R Ｋ’’ ) (R Ｌ ) is listed below in List 3a: 【Chemistry 26】 【Chemistry 27】 【Chemistry 28】 is defined in O1 to O328 are defined in List A as defined herein; V1 to V192 are listed in List B below: 【Chemistry 29】 【Transformation 30】 【Chemistry 31】 【Chemistry 32】 【Transformation 33】 【Transformation 34】 【Chemistry 35】 【Transformation 36】 2. The compound of claim 1, wherein:

5. The compound is M(L Ａ ) ｐ (L Ｂ ) ｑ (L Ｃ ) ｒ wherein L Ｂ and L Ｃ q is 0, 1, or 2; r is 0, 1, or 2; and p + q + r is the oxidation state of the metal M.

6. L Ｂ and L Ｃ each independently having the structure of List 4 below: 【Chemistry 37】 【Transformation 38】 (In the formula: T is selected from the group consisting of B, Al, Ga, and In; K １’ is a single bond, O, S, NR ｅ , P.R. ｅ , B.R. ｅ , C.R. ｅ R ｆ , and SiR ｅ R ｆ selected from the group consisting of: Y １ ~Y １３ each is independently selected from the group consisting of C and N; Y' is BR ｅ , B.R. ｅ R ｆ , N.R. ｅ , P.R. ｅ , P(O)R ｅ , O, S, Se, C=O, C=S, C=Se, C=NR ｅ , C=CR ｅ R ｆ , S=O, SO ２ , C.R. ｅ R ｆ , SiR ｅ R ｆ , and GeR ｅ R ｆ selected from the group consisting of: R ｅ and R ｆ can be fused or linked to form a ring; Each R ａ , R ｂ , R ｃ , and R ｄ independently represent one to the maximum number of substitutions allowed, 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 is independently hydrogen or a substituent selected from the group consisting of deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, selenyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; R ａ１ , R ｂ１ , R ｃ１ , R ｄ１ , R ａ , R ｂ , R ｃ , and R ｄ any two substituents of which may be fused or linked to form a ring or to form a multidentate ligand.

7. 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 formula Ir(L Ａ ) ２ (L Ｃｊ－ＩＩ ) L Ａ is according to formula I; k is an integer from 1 to 543; Each L Ｂｋ is the structure defined in Listing 6 below: 【Chemistry 39】 【Chemistry 40】 【Chemistry 41】 【Chemistry 42】 【Chemistry 43】 【Chemistry 44】 【Chemistry 45】 【Chemistry 46】 【Chemistry 47】 【Chemistry 48】 【Chemistry 49】 [Transformation 50] 【Chemistry 51】 【Chemistry 52】 【Chemistry 53】 【Chemistry 54】 【Transformation 55】 【Transformation 56】 【Chemistry 57】 【Transformation 58】 【Chemistry 59】 【Transformation 60】 【Chemistry 61】 【Transformation 62】 【Transformation 63】 【Chemistry 64】 【Transformation 65】 【Chemical Formula 66】 【Transformation 67】 【Transformation 68】 and Each L Ｃｊ－Ｉ is the expression 【Transformation 69】 and having a structure based on Each L Ｃｊ－ＩI is the expression 【Transformation 70】 and having a structure based on L Ｃｊ－Ｉ and L Ｃｊ－ＩＩ Each L in Ｃｊ About R ２０１ and R ２０２ are each independently selected from the following list 7: 【Chemistry 71】 【Chemistry 72】 【Transformation 73】 【Chemistry 74】 【Chemistry 75】 【Transformation 76】 【Chemical 77】 【Transformation 78】 as defined in R Ｄ１ ~R Ｄ２４６ is a structure defined in List C below: 【Transformation 79】 【Chemistry 80】 【Chemistry 81】 【Chemistry 82】 6. The compound of claim 5 having the formula:

8. The compound has the structure of List 9 below: 【Chemistry 83】 【Chemical 84】 【Chemical 85】 【Chemical 86】 【Chemistry 87】 【Chemical 88】 【Chemical 89】 [Chemical 90] 【Chemistry 91】 【Chemistry 92】 【Chemistry 93】 【Chemical 94】 【Chemical 95】 【Chemistry 96】 【Chemistry 97】 【Chem.98】 【Chem.99】 【Chemistry 100】 【Chemistry 101】 【Chemical Engineering 102】 【Chemistry 103】 【Chemical 104】 【Chemistry 105】 【Chemistry 106】 【Chemistry 107】 【Chemistry 108】 2. The compound of claim 1 selected from the group consisting of:

9. anode; a cathode; and an organic layer disposed between the anode and the cathode wherein the organic layer comprises a first ligand L Ａ and wherein the first ligand L Ａ has the structure of Formula I: 【Chemistry 109】 (In the formula, Moieties A and D are each independently a monocyclic ring or a polycyclic fused ring system, and each ring of the monocyclic ring or polycyclic fused ring system is independently a 5- to 10-membered carbocyclic or heterocyclic ring; The moiety C is a 5- or 6-membered carbocyclic or heterocyclic ring; Z １ , Z ２ and X １ ~X ４ each is independently C or N; Part A is X １ ~X ４ and said X １ ~X ４ one of which is C; Y is BR, BRR', NR, PR, P(O)R, O, S, Se, C=O, C=S, C=Se, C=NR', C=CRR', S=O, SO ２ , CR, CRR′, SiRR′, and GeRR′; K is 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 ) selected from the group consisting of; R Ａ , R Ｂ , R Ｃ , and R Ｄ each independently represents one to the maximum number of substitutions or no substitutions; Each R, R', R α , R β , R Ａ , R Ｂ , R Ｃ , and R Ｄ is independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boryl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, selenyl, and combinations thereof; At least one R Ｃ or R Ｄ is a substituent R containing a carbocyclic or heterocyclic group ＊ ) L Ａ is coordinated to the metal M; M is selected from the group consisting of Ir, Rh, Re, Ru, Os, Pt, Pd, Ag, Au, and Cu; M may be coordinated to other ligands; L Ａ may be combined with other ligands to comprise a tridentate, tetradentate, pentadentate, or hexadentate ligand; any two substituents may be joined or fused to form a ring; and Subject to the following conditions: (1) The moiety C is a six-membered ring and R Ｃ or R Ｄ is R ＊ If R ＊ is not an unsubstituted phenyl group or a phenyl group substituted with an electron-withdrawing group; (2) Moiety C and moiety D together form a naphthalene ring, and R Ｃ is R ＊ If R ＊ is not unsubstituted carbazole, 2,7-di-tert-butyl-carbazole, or 3,5-di-tert-butyl-carbazole; and (3) R Ｄ is R ＊ If R ＊ is an organic light emitting device (OLED) that is not selected from list RD as defined herein.

10. anode; a cathode; and an organic layer disposed between the anode and the cathode wherein the organic layer comprises a first ligand L Ａ and wherein the first ligand L Ａ has the structure of Formula I: 【Chemical 110】 (In the formula, Moieties A and D are each independently a monocyclic ring or a polycyclic fused ring system, and each ring of the monocyclic ring or polycyclic fused ring system is independently a 5- to 10-membered carbocyclic or heterocyclic ring; The moiety C is a 5- or 6-membered carbocyclic or heterocyclic ring; Z １ , Z ２ and X １ ~X ４ each is independently C or N; Part A is X １ ~X ４ and said X １ ~X ４ one of which is C; Y is BR, BRR', NR, PR, P(O)R, O, S, Se, C=O, C=S, C=Se, C=NR', C=CRR', S=O, SO ２ , CR, CRR′, SiRR′, and GeRR′; K is 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 ) selected from the group consisting of; R Ａ , R Ｂ , R Ｃ , and R Ｄ each independently represents one to the maximum number of substitutions or no substitutions; Each R, R', R α , R β , R Ａ , R Ｂ , R Ｃ , and R Ｄ is independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boryl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, selenyl, and combinations thereof; At least one R Ｃ or R Ｄ is a substituent R containing a carbocyclic or heterocyclic group ＊ wherein L Ａ is coordinated to the metal M; M is selected from the group consisting of Ir, Rh, Re, Ru, Os, Pt, Pd, Ag, Au, and Cu; M may be coordinated to other ligands; L Ａ may be combined with other ligands to comprise a tridentate, tetradentate, pentadentate, or hexadentate ligand; any two substituents may be joined or fused to form a ring; and Subject to the following conditions: (1) The moiety C is a six-membered ring and R Ｃ or R Ｄ is R ＊ If R ＊ is not an unsubstituted phenyl group or a phenyl group substituted with an electron-withdrawing group; (2) Moiety C and moiety D together form a naphthalene ring, and R Ｃ is R ＊ If R ＊ is not unsubstituted carbazole, 2,7-di-tert-butyl-carbazole, or 3,5-di-tert-butyl-carbazole; and (3) R Ｄ is R ＊ If R ＊ is a consumer product comprising an organic light emitting device (OLED) that is not selected from list RD defined herein.

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