Organic electroluminescent materials and devices

Abstract

The invention relates to organic electroluminescent materials and devices. A compound is provided that includes the structure of Formula I. In formula I, M is Pt, Pd or Au; part A is a 5-membered or 6-membered ring; each of the portions B, C and D is a monocyclic or polycyclic fused ring system; each of X1 to X6 and Z1 to Z3 is C or N; x9 is CRE or N; each of K1 and K2 is independently a direct bond or a linking group; each of L1 to L3 is a direct bond or a linking group; each R substituent is hydrogen or a universal substituent as defined herein; and at least one of RF and RF'is not hydrogen, and at least one of RG and RG 'is not hydrogen. Formulations, OLEDs, and consumer products containing the compounds are also provided.

Description

[0001] Cross Reference to Related Applications

[0002] This application claims priority to U.S. Provisional Application No. 63 / 643,191, filed May 6, 2024, pursuant to 35 U.S. SC §119(e), the entire contents of which are incorporated herein by reference. Technical Field

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

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

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

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

[0007] In one aspect, this disclosure provides a compound comprising the structure of formula I:

[0008] In Equation I:

[0009] M is Pt, Pd, or Au;

[0010] Each independently single or double bond;

[0011] moiety A is a 5- or 6-membered ring;

[0012] each of moiety B, moiety C, and moiety D is independently a monocyclic or a polycyclic fused ring system, wherein each ring in the monocyclic or the polycyclic fused ring system is independently a 5- to 10-membered carbocyclic or heterocyclic ring;

[0013] X 1 to X 8 , Z 1 , Z 2 , and Z 3 each independently is C or N;

[0014] X 9 is CR E or N;

[0015] K 1 and K 2 each independently is selected from the group consisting of a direct bond, O, S, N(R α ), P(R α ), B(R α ), C(R α )(R β ), and Si(R α )(R β );

[0016] L 1 to L 3 each independently is selected from the group consisting of a direct bond, BR, BRR', NR, PR, P(O)R, O, S, Se, C=O, C=S, C=Se, C=NR', C=CRR', S=O, SO2, CR, CRR', SiRR', and GeRR';

[0017] each of R A , R B , R C , and R D independently represents mono-substitution to the maximum allowable substitution, or no substitution;

[0018] each of R, R', R α , R β , R A , R B , R C , R D , R E , R F , R F' , R G' , and R G'each independently is hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfido, sulfinyl, sulfonyl, phosphino, selenoalkyl, and combinations thereof, wherein R F and at least one of R F' and at least one of R G and R G is not hydrogen; and

[0019] Any two substituents can be joined or fused together to form a ring.

[0020] In another aspect, the disclosure provides a formulation comprising a compound comprising a structure of Formula I as described herein.

[0021] In another aspect, the disclosure provides an OLED having an organic layer comprising a compound comprising a structure of Formula I as described herein.

[0022] In another aspect, the disclosure provides a consumer product comprising an OLED having an organic layer comprising a compound comprising a structure of Formula I as described herein. BRIEF DESCRIPTION OF DRAWINGS

[0023] Figure 1 An organic light emitting device is shown.

[0024] Figure 2 An inverted organic light emitting device without a separate electron transport layer is shown. DETAILED DESCRIPTION

[0025] A. Terminology

[0026] The following terms as used herein are defined as follows, unless otherwise specified:

[0027] As used herein, "top" means farthest from the substrate, and "bottom" means closest to the substrate. Where a first layer is described as "disposed on" a second layer, the first layer is disposed farther from the substrate than the second layer. Unless stated that the first layer is "in contact with" the second layer, there can be intervening layers between the first and second layers. For example, a cathode can be described as "disposed on" an anode even though various organic layers are between the cathode and the anode.

[0028] As used herein, "solution processible" means capable of being dissolved, dispersed, or transported in and / or deposited from a liquid medium, either in solution or suspension form.

[0029] As used herein, and as will be generally understood by one of ordinary skill 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. Since ionization potential (IP) is measured as a negative energy with respect to the vacuum energy level, a higher HOMO energy level corresponds to a smaller absolute value of IP (a less negative IP). Similarly, a higher LUMO energy level corresponds to a smaller absolute value of electron affinity (EA) (a less negative EA). On a conventional energy level diagram with the vacuum energy level at the top, a LUMO energy level of a material is higher than a HOMO energy level of the same material. A "higher" HOMO or LUMO energy level is thus represented by a more positive number on such a diagram, as it is closer to the top of the diagram.

[0030] As used herein, and as will be generally understood by one of ordinary skill in the art, a first work function has a "greater than" or "higher than" a second work function if the first work function has a higher absolute value. Since work functions are typically measured as negative numbers relative to the vacuum energy level, this means that a "higher" work function is more negative. On a conventional energy level diagram with the vacuum energy level at the top, a "higher" work function is thus illustrated as being further away from the vacuum energy level in the downward direction. Thus, the definitions of HOMO and LUMO energy levels follow different conventions than work functions.

[0031] Layers, materials, regions, and devices can be described herein with reference to the color of light emitted thereby. Generally, as used herein, an emissive region described as producing a particular color of light can include one or more emissive layers disposed in a stacked manner over one another.

[0032] As used herein, "NIR," "red," "green," "blue," "yellow" layers, materials, regions, or devices refer to layers, materials, regions, or devices that emit light in the wavelength range of about 700-1500 nm, 580-700 nm, 500-600 nm, 400-500 nm, 540-600 nm, respectively, or layers, materials, regions, or devices that have the highest emission spectrum peak in the corresponding wavelength region. In some arrangements, separate regions, layers, materials, or devices can provide separate "deep blue" and "light blue" emissions. As used herein, "deep blue" emission component refers to an emission with a peak emission wavelength that is at least about 4 nm less than the peak emission wavelength of a "light blue" emission component. Typically, the peak emission wavelength of a "light blue" emission component is in the range of about 465-500 nm, and the peak emission wavelength of a "deep blue" emission component is in the range of about 400-470 nm, although these ranges can vary for some configurations.

[0033] In some arrangements, color shifting layers are provided that convert, modify, or change the color of light emitted by another layer to an emission with a different wavelength. Such color shifting layers can be configured to shift the wavelength of light emitted by another layer by a defined amount, as measured by the difference in 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 removing light of non-desired wavelengths, and color shifting layers that convert higher energy photons to lower energy. For example, there can be a "red" filter in order to filter input light to remove light with wavelengths outside the range of about 580-700 nm. The component of "color" refers to a component that, when activated or in use, produces or otherwise emits light with a particular color as previously described. For example, "a first emission region of a first color" and "a second emission region of a second color different from the first color" describe two emission regions that emit two different colors as previously described when activated within a device.

[0034] As used herein, emission materials, layers, and regions can be distinguished from one another and from other structures based on the light that the material, layer, or region initially produces versus the light that the same or different structure ultimately emits. Initial light production is typically the result of an energy level change that results in photon emission. For example, an organic emission material can initially produce blue light, which can be converted to red or green light by a color filter, quantum dot, or other structure, such that the complete emission stack or sub-pixel emits red or green light. In this case, the initial emission material, region, or layer can be referred to as a "blue" component, even though the sub-pixel is a "red" or "green" component.

[0035] In some cases, it can be preferable to describe the color of components, such as the color of emissive regions, sub-pixels, color shifting layers, etc., in terms of 1931 CIE coordinates. For example, a yellow emissive material can have multiple peak emission wavelengths, one in or near the edge of the "green" region, and one within or near the edge of the "red" region, as previously described. Thus, as used herein, each color term also corresponds to a shape in the 1931 CIE coordinate color space. Shapes in the 1931 CIE color space are constructed by tracing the locus between two color points and any other interior point. For example, the interior shape parameters for red, green, blue, and yellow can be defined as follows:

[0036]

[0037] The terms "halo," "halogen," and "halide" are used interchangeably and refer to fluorine, chlorine, bromine, and iodine.

[0038] The term "acyl" refers to a substituted carbonyl (-C(O)-R s ).

[0039] The term "ester" refers to a substituted oxycarbonyl (-0-C(0)-R s or -C(0)-0-R s ) group.

[0040] The term "ether" refers to an -OR s group.

[0041] The terms "sulfanyl" or "sulfide" are used interchangeably and refer to an -SR s group.

[0042] The term "selenoalkyl" refers to a -SeR s group.

[0043] The term "sulfinyl" refers to a -S(0)-R s group.

[0044] The term "sulfonyl" refers to a -SO2-R s group.

[0045] The term "phosphino" refers to a group containing at least one phosphorus atom bonded to the rest of the molecule. Common examples of phosphino groups include, but are not limited to, groups such as -P(R s )2groups, or -PO(R s )2groups, where each R s may be the same or different.

[0046] The term "silyl" refers to a group containing at least one silicon atom bonded to the rest of the molecule. Common examples of silyl groups include, but are not limited to, groups such as -Si(R s)3group, where each R s may be the same or different.

[0047] The term "germyl" refers to a group containing at least one germanium atom bonded to the relevant structure. Common examples of germyl groups include, but are not limited to, groups such as -Ge(R s )3group, where each R s may be the same or different.

[0048] The term "boronyl" refers to a group containing at least one boron atom bonded to the relevant structure. Common examples of boronyl groups include, but are not limited to, groups such as -B(R s )2group or its Lewis adduct -B(R s )3group, where R s may be the same or different.

[0049] In each of the above, R s may be hydrogen or a substituent selected from the group consisting of the generic substituents as defined in this application. Preferably, R s is selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, and combinations thereof. More preferably, R s is selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0050] The term "alkyl" refers to and includes both straight- and branched-chain alkyl groups having alkyl carbon atoms bonded to the relevant structure. Preferred alkyl groups are alkyl groups containing 1 to 15 carbon atoms, preferably 1 to 9 carbon atoms, and preferred alkyl groups include methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, i-butyl, t-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. Additionally, the alkyl group can be further substituted.

[0051] The term "cycloalkyl" means and includes both monocyclic, polycyclic, and spirocyclic alkyl groups having a cycloalkyl carbon atom bonded to the relevant structure. Preferred cycloalkyl groups are cycloalkyl groups containing three to twelve 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. Additionally, the cycloalkyl group can be further substituted.

[0052] The term "heteroalkyl" or "heterocycloalkyl" means and includes 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. Additionally, the heteroalkyl or heterocycloalkyl group can be further substituted.

[0053] The term "alkenyl" means and includes both straight-chain and branched-chain alkenyl groups. An alkenyl group is essentially an alkyl group that includes at least one carbon-carbon double bond in the alkyl chain, where one carbon atom comes from the carbon-carbon double bond bonded to the relevant structure. A cycloalkenyl group is essentially a cycloalkyl group that includes at least one carbon-carbon double bond in the cycloalkyl ring. As used herein, the term "heteroalkenyl" means 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 two to fifteen carbon atoms. Additionally, the alkenyl, cycloalkenyl, or heteroalkenyl group can be further substituted.

[0054] The term "alkynyl" means and includes both straight-chain and branched-chain alkynyl groups. An alkynyl group is essentially an alkyl group that includes at least one carbon-carbon triple bond in the alkyl chain, where one carbon atom comes from the carbon-carbon triple bond bonded to the relevant structure. Preferred alkynyl groups are those containing two to fifteen carbon atoms. Additionally, the alkynyl group can be further substituted.

[0055] The terms "aralkyl" or "arylalkyl" are used interchangeably and mean an aryl-substituted alkyl group having an alkyl carbon atom bonded to the relevant structure. Additionally, the aralkyl group can be further substituted.

[0056] The term "heterocyclyl" means and includes both aromatic and non-aromatic ring 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 ring groups are used interchangeably with heteroaryl groups. Preferred non-aromatic heterocyclyl groups are non-aromatic heterocyclyl groups containing 3 to 10 ring atoms, preferably non-aromatic heterocyclyl groups containing 3 to 7 ring atoms including at least one heteroatom, and include cyclic amines, such as morpholinyl, piperidinyl, pyrrolidinyl, and the like, and cyclic ethers / sulfides, such as tetrahydrofuran, tetrahydropyran, tetrahydrothiophene, and the like. Additionally, the heterocyclyl groups can be further substituted or fused.

[0057] The term "aryl" means and includes both monocyclic and polycyclic aromatic hydrocarbon groups. Polycyclic rings can have two or more rings, in which two carbons are common to two adjacent rings (the rings are "fused"). Preferred aryl groups are aromatic groups containing six to thirty carbon atoms, preferably six to twenty-four carbon atoms, six to eighteen carbon atoms, and more preferably six to twelve carbon atoms. Especially preferred are aryl groups having six carbons, ten carbons, twelve carbons, fourteen carbons, or eighteen carbons. Suitable aryl groups include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthyl, anthracenyl, azulenyl, phenanthrenyl, pyrenyl, perylene, and azulene, preferably phenyl, biphenyl, terphenyl, triphenylene, and naphthyl. Additionally, the aryl groups can be further substituted or fused, such as, but not limited to fluorene.

[0058] The term "heteroaryl" means and includes both monocyclic aromatic groups and polycyclic aromatic ring systems having at least one heteroatom. Heteroatoms include, but are not limited to, O, S, Se, N, P, B, Si, Ge, and Se. In many cases, O, S, N, or B are preferred heteroatoms. Monocyclic heteroaromatic systems are preferably monocyclic rings having 5 or 6 ring atoms, and the ring can have one to six heteroatoms. Polycyclic heterocyclic systems can have two or more aromatic rings, where two atoms are common to two adjacent rings (the rings are "fused"), where at least one of the rings is heteroaryl. Polycyclic heteroaromatic ring systems can have one to six heteroatoms in each ring of the polycyclic aromatic ring system. Preferred heteroaryls are heteroaryls containing three to thirty carbon atoms, preferably three to twenty-four carbon atoms, three to eighteen carbon atoms, and more preferably three to twelve carbon atoms. Suitable heteroaryls include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolo-dipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazol, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furopyridine, benzothienopyridine, thienopyridine, benzoselenophenopyridine, selenophenopyridine, azaborine, borazine, 5λ 2 ,9λ 2 -diazaboro-13b-bora-naphthacene, 5λ 2 -benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, and 5,9-dioxa-13b-bora-naphthacene[3,2,1-de]anthracene; preferably dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 5λ 2 ,9λ 2 -diazaboro-13b-bora-naphthacene, 5λ 2 -benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, and 5,9-dioxa-13b-bora-naphthacene[3,2,1-de]anthracene. Additionally, the heteroaryl groups can be further substituted or fused.

[0059] 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-boronanaphene[2,3,4-de]anthracene, 5λ 2 -Benzo[d]benzo[4,5]imidazo[3,2-a]imidazo, 5,9-dioxa-13b-boronazona[3,2,1-de]anthracene groups, and each of their corresponding aza analogs are of particular interest.

[0060] In many cases, the general substituents are selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silalkyl, germanalkyl, boranalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, selenyl, sulfinyl, sulfonyl, phosphin, and combinations thereof.

[0061] In some cases, preferred general substituents are selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silalkyl, germanalkyl, boroalkyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thioyl, and combinations thereof.

[0062] In some cases, more preferred general substituents are selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, alkoxy, aryloxy, amino, silyl, germanyl, boronyl, aryl, heteroaryl, nitrile, thio, and combinations thereof.

[0063] In some cases, even more preferred general substituents are selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, silyl, aryl, heteroaryl, nitriles and combinations thereof.

[0064] In other cases, the most preferred general substituent is selected from the group consisting of: deuterium, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0065] The terms "substituted" and "substituted" refer to substituents other than H being bonded to the relevant position, such as carbon or nitrogen. For example, when R... 1 When representing monosubstitution, then an R 1 It must not be H (i.e., substitution). Similarly, when R 1 When representing disubstituted substitution, then the two Rs 1 It must not be H. Similarly, when R... 1 When R represents zero or no substitution, 1 For example, it could be hydrogen atoms with all available valences in the ring atom, such as carbon atoms in benzene and nitrogen atoms in pyrrole, or simply none for ring atoms with fully saturated valences, such as nitrogen atoms in pyridine. The maximum possible number of substitutions in a ring structure will depend on the total number of available valences in the ring atoms.

[0066] As used herein, "combination thereof" means that one or more members of the applicable list are combined to form a known or chemically stable arrangement that one of ordinary skill in the art could envision 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 haloalkyl substituent; and halogen, alkyl, and aryl can be combined to form a haloaralkyl group. In one example, the term substituted includes combinations of two to four of the listed groups. In another example, the term substituted includes combinations of two to three groups. In yet another example, the term substituted includes combinations of two groups. Preferred combinations of substituents are combinations containing up to fifty atoms that are not hydrogen or deuterium, or combinations including up to forty atoms that are not hydrogen or deuterium, or combinations including up to thirty atoms that are not hydrogen or deuterium. In many cases, preferred combinations of substituents will include up to twenty atoms that are not hydrogen or deuterium.

[0067] The "aza" designation in fragments described herein, i.e., aza-dibenzofurans, aza- dibenzothiophenes, and the like, means that one or more of the C-H groups in the corresponding aromatic ring can be replaced with a nitrogen atom, for example and without any limitation, aza-triphenylenes encompass dibenzo[f,h]quinoxaline and dibenzo[f,h]quinoline. Other nitrogen analogs of the aza-derivatives described above can be readily envisioned by one of ordinary skill in the art, and all such analogs are intended to be encompassed by the term as set forth herein.

[0068] As used herein, "deuterium" refers to an isotope of hydrogen. Deuterated compounds can be readily prepared using methods known in the art. For example, U.S. Patent No. 8,557,400, Patent Publication No. WO 2006 / 095951, and U.S. Patent Application Publication No. US2011 / 0037057, which are incorporated herein by reference in their entirety, describe the preparation of deuterium-substituted organometallic complexes. Further reference is made to Ming Yan, et al., Tetrahedron 2015, 71, 1425-30 and Atzrodt, et al., Angew. Chem. Int. Ed. (Review) 2007, 46, 7744-65, which are incorporated by reference in their entirety, describing efficient routes to deuterate methylene hydrogens in benzyl amines and replace aromatic ring hydrogens with deuterium, respectively.

[0069] As used herein, any specifically listed substituent, such as, but not limited to, methyl, phenyl, pyridyl, and the like, includes its non-deuterated, partially deuterated, and fully deuterated forms. Similarly, classes of substituents such as, but not limited to, alkyl, aryl, cycloalkyl, heteroaryl, and the like, also include their non-deuterated, partially deuterated, and fully deuterated forms. Unless otherwise specified, no atom in a chemical structure that has a valence of H or D completely filled should be considered to include its non-deuterated, partially deuterated, and fully deuterated forms. For example, a chemical structure means to include C6H6, C6D6, C6H3D3, and any other partially deuterated variant thereof. Some common, substantially partially or fully deuterated groups include, but are not limited to, CD3, CD2C(CH3)3, C(CD3)3, and C6D5.

[0070] It should be understood that when a fragment of a molecule is described as a substituent or otherwise attached to another moiety, its name can be written as if it were a fragment (e.g., phenyl, phenylene, naphthyl, dibenzofuranyl) or as if it were a whole molecule (e.g., benzene, naphthalene, dibenzofuran). As used herein, these different ways of naming substituents or attached fragments are considered equivalent.

[0071] In some cases, a pair of substituents in a molecule can optionally be joined or fused to form a ring. Preferred rings are five- to nine-membered carbocyclic or heterocyclic rings, including both cases where the portion of the ring formed by the pair of substituents is saturated and where the portion of the ring formed by the pair of substituents is unsaturated. In still other cases, a pair of adjacent substituents can optionally be joined or fused to form a ring. As used herein, “adjacent” means that the two substituents involved can be next to each other on the same ring, or on two adjacent rings having the two closest available substitutable positions (such as the 2,2’ positions in biphenyl or the 1,8 positions in naphthalene).

[0072] B. Compounds of the Disclosure

[0073] In one aspect, the disclosure provides a compound comprising the structure of Formula I:

[0074] In Formula I:

[0075] M is Pt, Pd, or Au;

[0076] each is independently a single or double bond;

[0077] moiety A is a 5- or 6-membered ring;

[0078] each of moiety B, moiety C, and moiety D is independently a monocyclic or polycyclic fused ring system, wherein each ring in the monocyclic or polycyclic fused ring system is independently a 5- to 10-membered carbocyclic or heterocyclic ring;

[0079] X 1 to X 6 , Z 1 , Z 2 and Z 3 each independently is C or N;

[0080] X 9 is CR E or N;

[0081] K 1 and K 2 each independently is selected from the group consisting of a direct bond, O, S, N(R α ), P(R α ), B(R α ), C(R α )(R β ), and Si(R α )(R β );

[0082] L 1 to L 3 each independently is selected from the group consisting of a direct bond, BR, BRR', NR, PR, P(O)R, O, S, Se, C=O, C=S, C=Se, C=NR', C=CRR', S=O, SO2, CR, CRR', SiRR', and GeRR';

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

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

[0085] wherein at least one of R F and R F' is not hydrogen, and at least one of R G and R G' is not hydrogen; and

[0086] Any two substituents can join or fuse together to form a ring.

[0087] In some embodiments, the compound consists essentially of Formula I. In some embodiments, the compound has the structure of Formula I.

[0088] In some embodiments, the compound has the structure of Formula I': wherein X 7 and X 8 each independently is C or N; and the remaining variables are the same as previously defined.

[0089] In some embodiments, at least one R A , R B , R C , R D , R E , R F , R F' , R G or R G' is selected from the group of generic substituents defined herein. In some embodiments, at least one R A is selected from the group of generic substituents defined herein. In some embodiments, at least one R B is selected from the group of generic substituents defined herein. In some embodiments, at least one R C is selected from the group of generic substituents defined herein. In some embodiments, at least one R D is selected from the group of generic substituents defined herein. In some embodiments, at least one R E is selected from the group of generic substituents defined herein. In some embodiments, at least one R F is selected from the group of generic substituents defined herein. In some embodiments, at least one R F' is selected from the group of generic substituents defined herein. In some embodiments, at least one R G is selected from the group of generic substituents defined herein. In some embodiments, at least one R G' is selected from the group of generic substituents defined herein. In some embodiments, at least one R A , R B , R C , R D , R E , R F , R F' , R G or R G' is selected from the group of preferred generic substituents defined herein.

[0090] In some embodiments of Formula I, at least one R, R', R α R β R A R B R C R D R E R F R F' R G and R G' It is partially or fully deuterated. In some embodiments, at least one R A It is partially or fully deuterated. In some embodiments, at least one R B It is partially or fully deuterated. In some embodiments, at least one R C It is partially or fully deuterated. In some embodiments, at least one R D It is partially or fully deuterated. In some embodiments, R E It is partially or fully deuterated. In some embodiments, R F Or R F' At least one of them is partially or fully deuterated. In some embodiments, R G Or R G' At least one of them is partially or fully deuterated. In some embodiments, at least one of R or R' is partially or fully deuterated.

[0091] In some embodiments, each of portions B, C, and D is independently a monocyclic or polycyclic fused ring system, wherein each ring of the monocyclic or polycyclic fused ring system is independently a 5- or 6-membered carbon ring or heterocyclic ring.

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

[0093] In some embodiments, ring A forms a metal-carbaene bond.

[0094] In some embodiments, X 7 With X 8 Between It is a double bond. In some embodiments, X 7 With X 8 Between It is a single key.

[0095] In some embodiments, the area between C and N of ring A It is a double bond. In some embodiments, the bond between the C and N atoms of ring A... It is a single key.

[0096] In some embodiments, R F and at least one of R F' is not hydrogen or deuterium, and at least one of R G and R G' is not hydrogen or deuterium.

[0097] In some embodiments, each of R, R', R α , R β , R A , R B , R C , R D , R E , R F , R F' , R G , R G' is independently hydrogen or a substituent selected from the group consisting of the preferred universal substituents. In some embodiments, each of R, R', R α , R β , R A , R B , R C , R D , R E , R F , R F' , R G , and R G' is independently hydrogen or a substituent selected from the group consisting of the more preferred universal substituents. In some embodiments, each of R, R', R α , R β , R A , R B , R C , R D , R E , R F , R F' , R G , and R G' is independently hydrogen or a substituent selected from the group consisting of the even more preferred universal substituents. In some embodiments, each of R, R', R α , R β , R A , R B , R C , R D , R E , R F , R F' , R G , and R G' is independently hydrogen or a substituent selected from the group consisting of the most preferred universal substituents.

[0098] In some embodiments, M is Pt. In some embodiments, M is Pd. In some embodiments, M is Au.

[0099] In some embodiments, each of Part B, Part C, and Part D is independently selected from the group consisting of the following cyclic moieties: benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, imidazole-derived carbene, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole, triazole, naphthalene, quinoline, isoquinoline, quinazoline, benzofuran, azabenzofuran, phenanthro[3,2-b]benzofuran, benzoxazole, azabenzoxazole, benzothiophene, azabenzothiophene, benzothiazole, azabenzothiazole, benzoselenophene, azabenzoselenophene, indene, azaindene, indole, azaindole, benzoimidazole, benzoimidazole-derived carbene, azabenzimidazole, benzo[9]benzoimidazole, azabeno[9]benzoimidazole, carbazole, azacarbazole, dibenzofuran, azadibenzofuran, dibenzothiophene, azadibenzothiophene, quinoxaline, phthalazine, phenanthrene, azaphenanthrene, anthracene, azanthracene, phenanthridine, fluorene, and azafiuorene. In some embodiments, the azabenzene variants include one N located on the benzo ring. In some embodiments, the azabenzene variants include one N located on the benzo ring and the N is bonded to the metal M.

[0100] In some embodiments, Ring A is selected from imidazole-derived carbene, pyrimidine, triazine,

[0101] In some embodiments, Part B is a monocyclic ring. In some embodiments, Part B is selected from the group consisting of benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, imidazole-derived carbene, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole, and triazole. In some embodiments, Part B is benzene.

[0102] In some embodiments, Part B is a polycyclic fused ring system. In some embodiments, Part B is selected from the group consisting of naphthalene, quinoline, isoquinoline, quinazoline, benzofuran, azabenzofuran, phenanthro[3,2-b]benzofuran, benzoxazole, azabenzoxazole, benzothiophene, azabenzothiophene, benzothiazole, azabenzothiazole, benzoselenophene, azabenzoselenophene, indene, azaindene, indole, azaindole, benzoimidazole, benzoimidazole-derived carbene, azabenzimidazole, benzo[9]benzoimidazole, azabeno[9]benzoimidazole, carbazole, azacarbazole, dibenzofuran, azadibenzofuran, dibenzothiophene, azadibenzothiophene, quinoxaline, phthalazine, phenanthrene, azaphenanthrene, anthracene, azanthracene, phenanthridine, fluorene, and azafiuorene. In some embodiments, Part B is naphthalene.

[0103] In some embodiments, moiety C is a monocyclic ring. In some embodiments, moiety C is selected from the group consisting of benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, imidazole-derived carbene, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole, and triazole. In some embodiments, moiety C is benzene.

[0104] In some embodiments, moiety C is a polycyclic fused ring system. In some embodiments, moiety C is selected from the group consisting of naphthalene, quinoline, isoquinoline, quinazoline, benzofuran, azabenzofuran, phenanthro[3 2-b]benzofuran, benzoxazole, azabenzoxazole, benzothiophene, azabenzothiophene, benzothiazole, azabenzothiazole, benzoselenophene, azabenzoselenophene, indene, azaindene, indole, azaindole, benzoimidazole, benzoimidazole-derived carbene, azabenzimidazole, benzo[9]benzoimidazole, azabeno[9]benzoimidazole, carbazole, azacarbazole, dibenzofuran, azadibenzofuran, dibenzothiophene, azadibenzothiophene, quinoxaline, phthalazine, phenanthrene, azaphenanthrene, anthracene, azanthracene, phenanthridine, fluorene, and azafiuorene. In some embodiments, moiety C is naphthalene.

[0105] In some embodiments, moiety C is or, together with L 2 forms a substituted or unsubstituted carbazole or 5λ 2 - benzo[d]benzo[4,5]imidazo[3,2-a]imidazole. In some embodiments, moiety C is a substituted or unsubstituted carbazole or 5λ 2 - benzo[d]benzo[4,5]imidazo[3,2-a]imidazole. In some embodiments, moiety C is or, together with L 2 forms a substituted or unsubstituted carbazole or 5λ 2 - benzo[d]benzo[4,5]imidazo[3,2-a]imidazole.

[0106] In some embodiments, moiety D is independently selected from the group consisting of pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, pyrazole, pyrrole, oxazole, thiazole, triazole, quinoline, isoquinoline, quinazoline, benzofuran, azabenzofuran, phenanthro[3 2-b]benzofuran, benzoxazole, azabenzoxazole, azabenzothiophene, benzothiazole, azabenzothiazole, azabenzoselenophene, indene, azaindene, indole, azaindole, benzoimidazole, azabenzimidazole, benzo[9]benzoimidazole, azabeno[9]benzoimidazole, azacarbazole, azadibenzofuran, azadibenzothiophene, quinoxaline, phthalazine, azaphenanthrene, azanthracene, phenanthridine, and azafiuorene.

[0107] In some embodiments, moiety D is a monocyclic ring. In some embodiments, moiety D is selected from the group consisting of pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, pyrazole, pyrrole, oxazole, thiazole, and triazole. In some embodiments, moiety D is pyridine.

[0108] In some embodiments, moiety D is a polycyclic fused ring system. In some embodiments, moiety D is selected from the group consisting of quinoline, isoquinoline, quinazoline, benzofuran, azabenzofuran, phenanthro[3,2-b]benzofuran, benzoxazole, azabenzoxazole, azabenzothiophene, benzothiazole, azabenzothiazole, azabenzoselenophene, indene, azaindene, indole, azaindole, benzimidazole, azabenzimidazole, benzo benzoimidazole, azabeno benzoimidazole, azacarbazole, azadibenzofuran, azadibenzothiophene, quinoxaline, phthalazine, azaphenanthrene, azanthracene, phenanthridine, and azaf luorene. In some embodiments, moiety D is naphthalene.

[0109] In some embodiments, moiety B and moiety C are benzene, and moiety D is pyridine.

[0110] In some embodiments, at least one of moiety B, moiety C, or moiety D can independently be a polycyclic fused ring structure. In some embodiments, at least one of moiety B, moiety C, or moiety 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 6-membered ring and one 5-membered ring. In some such embodiments, the 5-membered ring or the 6-membered ring can coordinate to the metal. In some embodiments, the polycyclic fused ring structure has two 6-membered rings. In some embodiments, at least one of moiety B, moiety C, or moiety D can independently be selected from the group consisting of benzofuran, benzothiophene, benzosele nophene, naphthalene, and azabenzofuran.

[0111] In some embodiments, at least one of moiety B, moiety C, or moiety 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 6-membered rings and one 5-membered ring. In some such embodiments, the 5-membered ring is fused to the ring coordinating to the metal M, and the second 6-membered ring is fused to the 5-membered ring. In some embodiments, at least one of moiety B, moiety C, or moiety D can independently be selected from the group consisting of dibenzofuran, dibenzothiophene, dibenzoselenophene, and azabenzofuran. In some such embodiments, at least one of moiety B, moiety C, or moiety D can independently be further substituted at the ortho or meta position of the O, S, or Se atom by a substituent selected from the group consisting of deuterium, fluorine, nitrile, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof. In some such embodiments, the azabenzofuran contains exactly one N atom at the 6-position (ortho to O, S, or Se) and a substituent at the 7-position (meta to O, S, or Se).

[0112] In some embodiments, at least one of moiety B, moiety C, or moiety 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 6-membered rings and one 5-membered ring. In some such embodiments, the 5-membered ring is fused to the ring coordinated to the metal M, the second 6-membered ring is fused to the 5-membered ring, and the third 6-membered ring is fused to the second 6-membered ring. In some such embodiments, the third 6-membered ring is further substituted with a substituent selected from the group consisting of deuterium, fluorine, nitrile, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0113] In some embodiments, at least one of moiety B, moiety C, or moiety 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 6-membered rings and one 5-membered ring or three 6-membered rings and two 5-membered rings. In some embodiments comprising two 5-membered rings, the 5-membered rings are fused together. In some embodiments comprising two 5-membered rings, the 5-membered rings are separated by at least one 6-membered ring. In some embodiments having one 5-membered ring, the 5-membered ring is fused to the ring coordinated to the metal M, the second 6-membered ring is fused to the 5-membered ring, the third 6-membered ring is fused to the second 6-membered ring, and the fourth 6-membered ring is fused to the third 6-membered ring.

[0114] In some embodiments, at least one of moiety B, moiety C, or moiety D can independently be an azaparalog of the polycyclic fused ring described above. In some such embodiments, at least one of moiety B, moiety C, or moiety D can independently contain exactly one azaparalog atom. In some such embodiments, at least one of moiety B, moiety C, or moiety D contains exactly two azaparalog atoms, which can be in one ring or in two different rings. In some such embodiments, the ring having the azaparalog N atom is separated from the metal M atom by at least two other rings. In some such embodiments, the ring having the azaparalog 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 azaparalog N atom is substituted.

[0115] In some embodiments, Z 1 and Z 2 are C. In some embodiments, either Z 1 or Z 2 is N, and the other of Z 1 or Z 2 is C.

[0116] In some embodiments, Z 3 is N. In some embodiments, Z 3 is carbenic. In some embodiments, Z 3 is C.

[0117] In some embodiments, X 1 each of X 6 is C.

[0118] In some embodiments, X 1 and X 2 are C. In some embodiments, at least one of X 1 or X 2 is N. In some embodiments, each of X 1 and X 2 is N.

[0119] In some embodiments, X 3 and X 4 are C. In some embodiments, at least one of X 3 or X 4 is N.

[0120] In some embodiments, X 5 and X 6 are C. In some embodiments, at least one of X 5 or X 6 is N.

[0121] In some embodiments, X 7 and X 8 are C. In some embodiments, at least one of X 7 or X 8 is N.

[0122] In some embodiments, K 1 is a direct bond. In some such embodiments, the carbene carbon atom is coordinated between the metal M and the two nitrogen atoms of ring A.

[0123] In some embodiments, K 1 is O or S. In some embodiments, K 1 is O. In some embodiments, K 1 is N(R α ), P(R α ), or B(R α ). In some embodiments, K 1 is C(R α )(R β ) or Si(R α )(R β ).

[0124] In some embodiments, K 2 is a direct bond.

[0125] In some embodiments, K 2 is O or S. In some embodiments, K2 is O. In some embodiments, K 2 is N(R α ), P(R α ), or B(R α ). In some embodiments, K 2 is C(R α )(R β ) or Si(R α )(R β ).

[0126] In some embodiments, K 1 and K 2 are both direct bonds. In some embodiments, K 1 is a direct bond and K 2 is not a direct bond. In some embodiments, K 1 is a direct bond and K 2 is O. In some embodiments, K 1 is not a direct bond and K 2 is a direct bond. In some embodiments, K 1 is O and K 2 is a direct bond.

[0127] In some embodiments, L 1 is a direct bond.

[0128] In some embodiments, L 1 is selected from the group consisting of O, S, and Se. In some embodiments, L 1 is O.

[0129] In some embodiments, L 1 is selected from the group consisting of BR, CR, SiRR, and GeRR. In some embodiments, L 1 is selected from the group consisting of P(O)R, C=O, C=S, C=Se, C=NR, C=CRR, S=O, and SO2. In some embodiments, L 1 is CR.

[0130] In some embodiments, L 1 is selected from the group consisting of BR, NR, and PR. In some embodiments, R is a substituted or unsubstituted aryl group. In some such embodiments, R is bonded or fused to R B or R C . In some embodiments, R is bonded or fused to R B . In some embodiments, R is bonded or fused to R C . In some embodiments, R is not bonded or fused to R B or R C . In some embodiments, L1 is NR.

[0131] In some embodiments, L 2 is a direct bond.

[0132] In some embodiments, L 2 is selected from the group consisting of O, S, and Se. In some embodiments, L 2 is selected from the group consisting of BR, CRR, SiRR, and GeRR. In some embodiments, L 2 is selected from the group consisting of P(O)R, C=O, C=S, C=Se, C=NR, C=CRR, S=O, and SO2. In some embodiments, L 2 is CR.

[0133] In some embodiments, L 2 is selected from the group consisting of BR, NR, and PR. In some embodiments, L 2 is NR. In some embodiments, R is a substituted or unsubstituted aryl. In some embodiments, R is bonded or fused with R C . In some embodiments, R is bonded or fused with R D . In some embodiments, R is bonded or fused with R C . In some embodiments, R is bonded or fused with R C to form a substituted or unsubstituted carbazole or 5λ 2 -benzo[d]benzo[4,5]imidazo[3,2-a]imidazole.

[0134] In some embodiments, L 2 is BR, BRR, NR, PR, P(O)R, C=NR, C=CRR, S=O, SO2, CR, CRR, SiRR, or GeRR, and L 2 R or R' is bonded or fused with R C or R D to form a ring.

[0135] In some embodiments, L 3 is a direct bond.

[0136] In some embodiments, L 3 is selected from the group consisting of O, S, and Se. In some embodiments, L 3 is selected from the group consisting of BR, CRR, SiRR, and GeRR. In some embodiments, L 3 is selected from the group consisting of P(O)R, C=O, C=S, C=Se, C=NR, C=CRR, S=O, and SO2. In some embodiments, L 3 is Cr.

[0137] In some embodiments, L 3 is selected from the group consisting of BR, NR, and PR. In some embodiments, L 3 is NR. In some embodiments, R is a substituted or unsubstituted aryl group. In some embodiments, R is bonded or fused to R A or R B . In some embodiments, R is bonded or fused to R B . In some embodiments, R is bonded or fused to R B to form a substituted or unsubstituted carbazole or 5Λ 2 -benzo[d]benzo[4,5]imidazo[3,2-a]imidazole.

[0138] In some embodiments, L 1 is O; L 2 is NR, where R is a substituted or unsubstituted aryl group bonded or fused to R C to form a substituted or unsubstituted carbazole; and L 3 is a direct bond. In some embodiments, L 1 is O; L 2 is NR, where R is a substituted or unsubstituted aryl group bonded or fused to R C to form a substituted or unsubstituted 5Λ 2 -benzo[d]benzo[4,5]imidazo[3,2-a]imidazole; and L 3 is a direct bond.

[0139] In some embodiments, X 9 is N.

[0140] In some embodiments, X 9 is CR E .

[0141] SPEC: In some embodiments, R E is hydrogen. In some embodiments, R E is partially or fully deuterated. In some embodiments, R E is partially or fully fluorinated.

[0142] In some embodiments, R E comprises a chemical group selected from the group consisting of silyl, germyl, aryl, heteroaryl, cycloalkyl, and heteroalkyl.

[0143] In some embodiments, R E comprises a moiety selected from the group consisting of aryl and heteroaryl. In some embodiments, R Ecomprises a moiety selected from the group consisting of benzene, pyridine, pyrimidine, pyridazine, pyrazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole, naphthalene, quinoline, isoquinoline, quinazoline, benzofuran, benzoxazole, benzothiophene, benzothiazole, benzoselenophene, indene, indole, benzimidazole, carbazole, diphenylene furan, diphenylene thiophene, quinoxaline, phthalazine, phenanthrene, phenanthridine, and fluorene. In some embodiments, R E is a partially or fully deuterated aryl group.

[0144] In some embodiments, R E comprises a silyl group. In some such embodiments, the silyl group is Si(Ph)3, which can be non-deuterated, partially deuterated, or fully deuterated. As used herein, Ph represents a phenyl group.

[0145] In some embodiments, R E is an electron-withdrawing group. In some embodiments, R E is F. In some embodiments, R E is CN. In some embodiments, R E is a nitrile.

[0146] In some embodiments, R E is adamantyl. In some embodiments, R E is an adamantane-containing group. In some embodiments, R E is an aliphatic bicyclic fused ring structure. In some embodiments, R E comprises a borane-containing ring structure. In some embodiments, R E comprises a polycyclic fused ring structure comprising three or more fused rings.

[0147] In some embodiments, the compound comprises an electron-withdrawing group. In some embodiments, the electron-withdrawing group has a Hammett constant greater than 0. In some embodiments, the Hammett constant of the electron-withdrawing group is equal to or greater than 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, or 1.1.

[0148] In some embodiments, the compound comprises an electron-withdrawing group selected from the group consisting of the following EWG1list of structures: 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 carbazolium, 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 pyridoxal, substituted or unsubstituted triazine, substituted or unsubstituted oxazole, substituted or unsubstituted benzoxazole, substituted or unsubstituted thiazole, substituted or unsubstituted benzothiazole, substituted or unsubstituted imidazole, substituted or unsubstituted benzimidazole, ketone, carboxylic acid, ester, nitrile, isonitrile, sulfinyl, sulfonyl, partially and fully fluorinated alkyl, partially and fully fluorinated aryl, partially and fully fluorinated heteroaryl, cyano-containing alkyl, cyano-containing aryl, cyano-containing heteroaryl, isocyanate,

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

[0150] wherein Y G is selected from the group consisting of BR e , NR e , PR e , O, S, Se, C=0, S=0, S02, CR e R f , SiR e R f , and GeR e R f' ; and

[0151] wherein each of R k1 , R k2 , R k3 , R e , and R f is independently hydrogen or a substituent selected from the group consisting of the generic substituents defined herein.

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

[0153] In some embodiments, the compound comprises an electron-withdrawing group selected from the group consisting of the structures in the following list of EWG3:

[0154] In some embodiments, the compound comprises an electron- withdrawing group selected from the group consisting of the following list of EWG4:

[0155] In some embodiments, the compound comprises a pi-electron deficient electron- withdrawing group selected from the group consisting of the following list of Pi-EWG: CN, COCH3, CHO, COCF3, COOMe, COOCF3, NO2, SF3, SiF3, PF4, SF5, OCF3, SCF3, SeCF3, SOCF3, SeOCF3, SO2F, SO2CF3, SeO2CF3, OSeO2CF3, OCN, SCN, SeCN, NC, + N(R k2 )3, BR k2 R k3 , substituted or unsubstituted diphenyleneborol, 1 -substituted carbazole, 1,9- substituted carbazole, substituted or unsubstituted carbazole, substituted or unsubstituted pyridine, substituted or unsubstituted pyrimidine, substituted or unsubstituted pyrazine, substituted or unsubstituted pyridazine, substituted or unsubstituted triazine, substituted or unsubstituted oxazole, substituted or unsubstituted benzoxazole, substituted or unsubstituted thiazole, substituted or unsubstituted benzothiazole, substituted or unsubstituted imidazole, substituted or unsubstituted benzimidazole, ketone, carboxylic acid, ester, nitrile, isonitrile, sulfinyl, sulfonyl, partially and fully fluorinated aryl, partially and fully fluorinated heteroaryl, cyano-containing aryl, cyano-containing heteroaryl, isocyanate, wherein the variables are the same as previously defined.

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

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

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

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

[0160] In some embodiments, R E is or comprises an electron-withdrawing group from the list of EWG1 as defined herein. In some embodiments, R E is or comprises an electron-withdrawing group from the list of EWG2 as defined herein. In some embodiments, R E is or comprises an electron-withdrawing group from the list of EWG3 as defined herein. In some embodiments, R Eis or comprises an electron-withdrawing group in the list of EWG4 as defined herein. In some embodiments, R E is or comprises an electron-withdrawing group in the list of PI-EWG as defined herein.

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

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

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

[0164] In some embodiments, the compound can have the structure of Formula X:

[0165]

[0166] wherein:

[0167] each of A1to A4is independently C or N;

[0168] the remaining variables are the same as previously defined; and

[0169] any two substituents can be joined or fused to form a ring.

[0170] In some embodiments, R F , R F' , R G , or R G' comprises a chemical group comprising at least three 6-membered aromatic rings that are not fused to one another. In some embodiments, at least two of R F , R F' , R G , or R G' comprise a chemical group comprising at least three 6-membered aromatic rings that are not fused to one another.

[0171] In some embodiments, at least one of R F , R F' , R G , or R G' comprises a chemical group comprising at least four 6-membered aromatic rings that are not fused to one another. In some embodiments, at least two of R F , R F' , R G , or R G' comprise a chemical group comprising at least four 6-membered aromatic rings that are not fused to one another.

[0172] In some embodiments, at least one of R F , R F' , R G , or R G'at least one of R F , R F' , R G , or R G' comprises a chemical group containing at least five 6-membered aromatic rings that are not fused to one another.

[0173] In some embodiments, at least one of R F , R F' , R G , or R G' comprises a chemical group containing at least six 6-membered aromatic rings that are not fused to one another. In some embodiments, at least two of R F , R F' , R G , or R G' comprises a chemical group containing at least six 6-membered aromatic rings that are not fused to one another.

[0174] In some embodiments, one of R F or R G comprises a chemical group containing three to six 6-membered aromatic rings that are not fused to one another, and one of R F' or R G' comprises a chemical group containing at least three to six 6-membered aromatic rings that are not adjacent to one another. In some embodiments, each of R F , R F' , R G , or R G' independently comprises a chemical group containing three to six 6-membered aromatic rings that are not fused to one another.

[0175] In some embodiments, at least one of R F , R F , R G , or R G' comprises a group R W , wherein R W has a structure selected from the group consisting of Formula XIA, A (R 1a )(R 2a ) a (R 3a ) b , Formula XIB, and Formula XIC wherein:

[0176] each of X 130 to X 138 is independently C or N;

[0177] Y S, Y T and each of Y U is independently CRR', SiRR', or GeRR';

[0178] n is an integer from 1 to 8,

[0179] each Y S may be the same or different;

[0180] Q A is selected from the group consisting of C, Si, Ge, N, P, O, S, Se, and B;

[0181] each of a and b is independently 0 or 1;

[0182] if Q A is C, Si, or Ge, then a + b = 2;

[0183] if Q A is N or P, then a + b = 1;

[0184] if Q A is B, then a + b can be 1 or 2;

[0185] if Q A is O, S, or Se, then a + b = 0;

[0186] each of R SS , R TT , and R UU independently represents mono-substitution to the maximum number of substitutions allowed, or no substitution;

[0187] each R, R', R 1a , R 2a , R 3a , R SS , R TT , and R UU is independently hydrogen or a substituent selected from the group consisting of the generic substituents defined herein; and

[0188] any two substituents can be fused or joined to form a ring.

[0189] In some embodiments, each of A1to A4is C. In some embodiments, one of A1to A4is N.

[0190] In some embodiments, at least one Y S , Y T , or Y U is SiRR' or GeRR'. In some embodiments, each Y S , Y T , and Y UIt is CRR'.

[0191] In some embodiments, the compound may have the structure of formula XII:

[0192]

[0193] in

[0194] A5 to A 12 Each is independently C or N; R EE Indicates single substitution up to the maximum permissible number of substitutions, or no substitution;

[0195] Each R EE It is independently hydrogen or a substituent selected from the group of general substituents as defined herein; and any two substituents may join or fuse to form a ring.

[0196] In some embodiments, A5 to A 12 Each of them is C. In some embodiments, A5 to A 12 One of them is N. In some embodiments, A5 to A 12 Both of them are N.

[0197] In some embodiments, each of A1 to A3 is C. In some embodiments, one of A1 to A3 is N.

[0198] In some embodiments, each of A5 to A8 is C. In some embodiments, one of A5 to A8 is N.

[0199] In some embodiments, A9 to A 12 Each of them is C. In some embodiments, A9 to A 12 One of them is N.

[0200] In some embodiments, the compound comprises the structure of formula II.

[0201] In some embodiments, if R F It is H and R F' If it is CD3, then R G Not -CD3, tert-butyl, or isobutyl. In some embodiments, R F It is H and R F' It's CD3.

[0202] In some embodiments, if R F It is H and R F' If it is a phenyl group, then R G and R G' Not all of them are CH3, CD3, or tert-butyl. In some embodiments, R F It is H and RF' is phenyl.

[0203] In some embodiments, if each of R F , R G , and R G' is CD3, then R F' is not CD3, phenyl-d5, 3-tert-butyl-phenyl, 3,5-di-tert-butyl-phenyl, or 3-tert-butyl-5-phenyl-phenyl. In some embodiments, R F , R G , and R G' are CD3.

[0204] In some embodiments, if each of R F and R F' is CD3, then R G and R G' are not both tert-butyl or phenyl. In some embodiments, R F and R F' are CD3.

[0205] In some embodiments, if each of R F and R F' is isobutyl-d9, then R G and R G' are not both CD3, tert-butyl, or phenyl. In some embodiments, R F and R F' are isobutyl-d9.

[0206] In some embodiments, R E is H. In some embodiments, R E is selected from the group consisting of the generic substituents defined herein. In some embodiments, R E is selected from the group consisting of the preferred generic substituents defined herein.

[0207] In some embodiments, if X 9 is CH and R F and R F' are both unsubstituted phenyl, then R G and R G' are not both methyl. In some embodiments, X 9 is CH and R F and R F' are both unsubstituted phenyl.

[0208] In some embodiments, R F and R G are fused to comprise a structure of Formula IA wherein Y 1 is O, S, or NR. In some embodiments, Y1 is O. In some embodiments, Y 1 is S. In some embodiments, Y 1 is NR.

[0209] In some embodiments, R F' and R G' are fused to comprise a structure of Formula IB wherein Y 2 is O, S, or NR. In some embodiments, Y 2 is O. In some embodiments, Y 2 is S. In some embodiments, Y 2 is NR.

[0210] In some embodiments, if R F and R G are fused to comprise a structure of Formula IA and R F' and R G' are fused to comprise a structure of Formula IB then the structure comprising ring E and its substituents R E , R F , R F' , R G , and R G' do not have a plane of symmetry from N of ring A to X 9 .

[0211] In some embodiments, if R G = R F = H and R G' = tBu, then R F' is not phenyl, D5-phenyl, 4-t-butylphenyl, 3,5-di-t-butylphenyl, 3-biphenyl, 4-biphenyl, 3,5-tribiphenyl, CD3, D7-iso-propyl, or D9-iso-butyl. As used herein, tBu represents a t-butyl group.

[0212] In some embodiments, if R G = R F = H and R G' = iso-butyl or D9-iso-butyl, then RF’ is not CD3, phenyl, iso-butyl, or D9-iso-butyl.

[0213] In some embodiments, if R G = R F = H and R G' = phenyl, D5-phenyl, or 3-tBu phenyl, then R F' is not CD3, D7-iso-propyl, D9-iso-butyl, or phenyl.

[0214] In some embodiments, when R G = H, R G' = phenyl or D5-phenyl, and R F = CD3, then R F' is not CD3.

[0215] In some embodiments, at least one R A is not hydrogen.

[0216] In some embodiments, at least one R A comprises at least one C atom. In some embodiments, at least one R A comprises at least two C atoms. In some embodiments, at least one R A comprises at least three C atoms. In some embodiments, at least one R A comprises at least four C atoms.

[0217] In some embodiments, at least one R A comprises a substituent selected from the group consisting of alkyl, cycloalkyl, silyl, germyl, aryl, heteroaryl, and combinations thereof.

[0218] In some embodiments, two R A are joined or fused to form a moiety A1 that is fused to ring A, wherein moiety A1 is a monocyclic or polycyclic fused ring system, wherein each ring in the monocyclic or polycyclic fused ring system is independently a 5- to 10-membered carbocyclic or heterocyclic ring.

[0219] In some embodiments, moiety A1 is selected from the list of cyclic moieties defined herein.

[0220] In some embodiments, moiety A1 is monocyclic. In some embodiments, moiety A1 is selected from the group consisting of benzene, pyridine, pyrimidine, pyridazine, pyrazine, imidazole, imidazole-derived carbene, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole, and triazole. In some embodiments, moiety A1 is benzene.

[0221] In some embodiments, moiety A1 is polycyclic fused ring system. In some embodiments, moiety A1 is selected from the group consisting of naphthalene, quinoline, isoquinoline, quinazoline, benzofuran, azabenzofuran, benzoxazole, azabenzoxazole, benzothiophene, azabenzothiophene, benzothiazole, azabenzothiazole, benzoselenophene, azabenzoselenophene, indene, azaindene, indole, azaindole, benzimidazole, benzimidazole-derived carbene, azabenzimidazole, carbazole, azacarbazole, dibenzofuran, azadibenzofuran, dibenzothiophene, azadibenzothiophene, quinoxaline, phthalazine, phenanthrene, azaphenanthrene, anthracene, azanthracene, phenanthridine, fluorene, and azafiuorene. In some embodiments, moiety A1 is naphthalene.

[0222] In some embodiments, at least one R B is not hydrogen. In some embodiments, at least one R B comprises at least one C atom. In some embodiments, at least one R B comprises at least two C atoms. In some embodiments, at least one R B comprises at least three C atoms. In some embodiments, at least one R B comprises at least four C atoms.

[0223] In some embodiments, at least one R B comprises a substituent selected from the group consisting of alkyl, cycloalkyl, silyl, germyl, aryl, heteroaryl, and combinations thereof.

[0224] In some embodiments, at least one R C is not hydrogen. In some embodiments, at least one R C comprises at least one C atom. In some embodiments, at least one R C comprises at least two C atoms. In some embodiments, at least one R C comprises at least three C atoms. In some embodiments, at least one R C comprises at least four C atoms.

[0225] In some embodiments, at least one R C comprises a substituent selected from the group consisting of alkyl, cycloalkyl, silyl, germyl, aryl, heteroaryl, and combinations thereof.

[0226] In some embodiments, at least one R D is not hydrogen. In some embodiments, at least one R D comprises at least one C atom. In some embodiments, at least one R D comprises at least two C atoms. In some embodiments, at least one R D comprises at least three C atoms. In some embodiments, at least one R D comprises at least four C atoms.

[0227] In some embodiments, at least one R D comprises a substituent selected from the group consisting of alkyl, cycloalkyl, silyl, germyl, aryl, heteroaryl, and combinations thereof.

[0228] In some embodiments, R E is present and is not hydrogen. In some embodiments, R E is present and comprises at least one C atom. In some embodiments, R Eis present and comprises at least two C atoms. In some embodiments, R E is present and comprises at least three C atoms. In some embodiments, R E is present and comprises at least four C atoms.

[0229] In some embodiments, R E is present and comprises a substituent selected from the group consisting of alkyl, cycloalkyl, silyl, germyl, aryl, heteroaryl, and combinations thereof.

[0230] In some embodiments, R E is present and is hydrogen. In some embodiments, R E is present and is deuterium.

[0231] In some embodiments, R E is selected from the group consisting of halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfido, sulfinyl, sulfonyl, phosphino, selenoalkyl, and combinations thereof. In some embodiments, R E is not H or D. In some embodiments, R E is alkyl, cycloalkyl, aryl, or heteroaryl. In some embodiments, R E is C6H5, C6D5, C(CH3)3, C(CD3)3, CD2C(CH3)3, CH3, CD3, cyclopentyl, cyclohexyl, or neopentyl.

[0232] In some embodiments, at least one R F or R F' is not hydrogen. In some embodiments, R F and R F' are not both hydrogen.

[0233] In some embodiments, at least one R F or R F' comprises at least one C atom. In some embodiments, at least one R F or R F' comprises at least two C atoms. In some embodiments, at least one R F or R F' comprises at least three C atoms. In some embodiments, at least one R F or R F' comprises at least four C atoms.

[0234] In some embodiments, at least one R F or R F'comprises a substituent selected from the group consisting of alkyl, cycloalkyl, silyl, germyl, aryl, heteroaryl, and combinations thereof. In some embodiments, at least one R F and R F' independently comprise a substituent selected from the group consisting of alkyl, cycloalkyl, silyl, germyl, aryl, heteroaryl, and combinations thereof. In some embodiments, at least one R F or R F' comprises an aryl substituent. In some embodiments, at least one R F or R F' comprises a silyl substituent.

[0235] In some embodiments, at least one R G or R G' is not hydrogen. In some embodiments, R G and R G' are not both hydrogen.

[0236] In some embodiments, at least one R G or R G' comprises at least one C atom. In some embodiments, at least one R G or R G' comprises at least two C atoms. In some embodiments, at least one R G or R G' comprises at least three C atoms. In some embodiments, at least one R G or R G' comprises at least four C atoms.

[0237] In some embodiments, at least one R G or R G' comprises a substituent selected from the group consisting of alkyl, cycloalkyl, silyl, germyl, aryl, heteroaryl, and combinations thereof. In some embodiments, R G and R G' each independently comprise a substituent selected from the group consisting of alkyl, cycloalkyl, silyl, germyl, aryl, heteroaryl, and combinations thereof. In some embodiments, at least one R G or R G' comprises an aryl substituent. In some embodiments, at least one R G or R G' comprises a silyl substituent.

[0238] In some embodiments, X 9 is CR E , R F is H, and R F' , R G , and R G'each of R E is H. In some embodiments, each of R F' , R G , and R G' comprises at least one C atom.

[0239] In some embodiments, X 9 is CR E , and each of R F , R F' , R G , and R G' is a non-H substituent. In some embodiments, R E is H. In some embodiments, each of R F , R F' , R G , and R G' comprises at least one C atom.

[0240] In some embodiments, R F and R G do not join to form a ring.

[0241] In some embodiments, R F' and R G' do not join to form a ring.

[0242] In some embodiments, each of R F and R F' is a substituted aryl group. In some embodiments, each of R F and R F' is a substituted benzene.

[0243] In some embodiments, at least one of R F or R F' is a substituted or unsubstituted heteroaryl group.

[0244] In some embodiments, each of R F and R F' is a silyl group. In some embodiments, one of R F or R F' comprises a silyl group.

[0245] In some embodiments, one of R F or R F' is a tert-butyl group. In some embodiments, one of R F or R F' is a neopentyl or deuterated neopentyl group. In some embodiments, one of R F or R F'One of them is an alkyl or deuterated alkyl group, and R G Or R G' One of them is aryl or deuterated aryl.

[0246] In some embodiments, R F and R F' Same. In some embodiments, R F and R F' different.

[0247] In some embodiments, R G and R G' Same. In some embodiments, R G and R G' different.

[0248] In some embodiments, R F R F' R G and R G' Each of them is independently partially or fully deuterated. In some embodiments, R F R F' R G and R G' Each of them is independently partially deuterated. In some embodiments, R F R F' R G and R G' Each of them is independently fully deuterated.

[0249] In some embodiments, R F R F' R G and R G' Neither is hydrogen nor deuterium. In some embodiments, R F Or R G Neither is hydrogen nor deuterium. In some embodiments, R F' Or R G Neither is hydrogen nor deuterium. In some embodiments, R F' Or R G' Neither is hydrogen nor deuterium. In some embodiments, R F and R G Same. In some embodiments, R F and R G Different. In some embodiments, R F' and R G' Same. In some embodiments, R F' and R G' different.

[0250] In some embodiments of Formula II, R F Or R F'at least one of R F or R F' at least one of R F or R F' at least one of R F or R F' at least one of R F and R F' each independently comprises a chemical group containing at least three to six 6-membered aromatic rings that are not fused to one another.

[0251] In some embodiments, at least one of R F or R F' comprises a structure selected from the group consisting of Formula XIIIA, Formula XIIIB, and Formula XIIIC, as defined herein.

[0252] In some embodiments of Formula II, Formula X, or Formula XII, at least one R A , R B , R C , R D , R E , R EE , R F , R F' , R G , or R G' is selected from the group consisting of the generic substituents defined herein. In some embodiments, at least one R A is selected from the group consisting of the generic substituents defined herein. In some embodiments, at least one R B is selected from the group consisting of the generic substituents defined herein. In some embodiments, at least one R C is selected from the group consisting of the generic substituents defined herein. In some embodiments, at least one R D is selected from the group consisting of the generic substituents defined herein. In some embodiments, at least one R E is selected from the group consisting of the generic substituents defined herein. In some embodiments, at least one R EE is selected from the group consisting of the generic substituents defined herein. In some embodiments, at least one R F is selected from the group consisting of the generic substituents defined herein. In some embodiments, at least one R F'is selected from the group consisting of the generic substituents defined herein. In some embodiments, at least one R G is selected from the group consisting of the generic substituents defined herein. In some embodiments, at least one R G' is selected from the group consisting of the generic substituents defined herein. In some embodiments, at least one R A , R B , R C , R D , R E , R EE , R F , R F' , R G or R G' is selected from the group consisting of the preferred generic substituents defined herein.

[0253] In some embodiments, the combination of moiety C-L 2 moiety D has a structure selected from the group consisting of the structures of List 1 below:

[0254] wherein:

[0255] T is selected from the group consisting of B, Al, Ga, and In;

[0256] K 1' is selected from the group consisting of a single bond, O, S, NR e , PR e , BR e , CR e R f , and SiR e R f ;

[0257] Y 1 is independently selected from the group consisting of C and N; 13

[0258] Y' is selected from the group consisting of BR e , BR e R f , NR e , PR e , P(O)R e , O, S, Se, C=O,

[0259] 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 ;

[0260] R e and R f may be fused or joined to form a ring;

[0261] each R a , R b , R c , and R d independently represents mono-substitution to the maximum number of substitutions allowed, or no substitution;

[0262] each of 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 generic substituents defined herein; and

[0263] any two adjacent substituents of R a1 , R b1 , R c1 , R d1 , R a , R b , R c , and R d may be fused or joined to form a ring or to form a polydentate ligand.

[0264] In some embodiments, the combination of moiety C-L 2 - moiety D has a structure selected from the group consisting of the structures of List 2 below:

[0265]

[0266]

[0267]

[0268]

[0269]

[0270] wherein:

[0271] R a ', Rb ' and R c ' and R d ' and R e each independently represents zero, single substitution or up to the maximum allowed number of substitutions of the ring to which it is attached;

[0272] R a ' and R b ' and R c ' and R d ' and R e each independently is hydrogen or a substituent selected from the group consisting of the generic substituents defined herein; and

[0273] R a ' and R b ' and R c ' and R d ' and R e two substituents of R A' are fused or joined to form a ring or to form a polydentate ligand. In some embodiments, the compound is selected from the group consisting of compounds of formula Pt(L A' (Ly) :

[0274]

[0275] wherein L y is selected from the group consisting of the structures of List 3 below:

[0276]

[0277]

[0278] wherein L y is selected from the group consisting of the structures of List 4 below:

[0279]

[0280]

[0281]

[0282]

[0283] wherein:

[0284] R E' represents di-substitution up to the maximum allowed substitution;

[0285] R E” represents mono-substitution up to the maximum allowed substitution;

[0286] each R E' , R E” , RH , R H' , R X , and R Y are independently hydrogen or a substituent selected from the group of generic substituents defined herein;

[0287] Any two substituents can be joined or fused together to form a ring.

[0288] In some embodiments, each R A , R B , R C , R D , R E' , R E” , R H , R H' , R X , and R Y are independently selected from the group consisting of the structures of List 5 below: and

[0289] wherein each R', R", R a1 , and R a2 is independently hydrogen or a substituent selected from the group of generic substituents defined herein.

[0290] In some embodiments, the compound has a structure selected from the group consisting of the structures of List 6 below:

[0291]

[0292]

[0293]

[0294]

[0295] wherein R A1 , R A2 , R B1 , R B2 , R C1 , R C2 , R D1 , R D2 , RE1 , R FF1 , R FF2 , R FF3 , R GG1 , R GG2 , R H1 , and R H2 each independently is hydrogen or a substituent selected from the group consisting of the generic substituents defined herein.

[0296] In some embodiments, each of R A1 , R A2 , R B1 , R B2 , R C1 , R C2 , R D1 , R D2 , R E1 , R FF1 , R FF2 , R FF3 , R GG1 , R GG2 , R H1 , and R H2 is independently hydrogen or a substituent selected from the group consisting of the preferred generic substituents defined herein.

[0297] In some embodiments, each of R A1 , R A2 , R B1 , R B2 , R C1 , R C2 , R D1 , R D2 , R E1 , R FF1 , R FF2 , R FF3 , R GG1 , R GG2 , R H1 , and R H2 is independently selected from the group consisting of List 5 defined herein.

[0298] In some embodiments, the compound is selected from the group consisting of compounds of formula Pt(L A' )(Ly):

[0299]

[0300] wherein L A' is selected from the group consisting of: [L A' i-(Ri)(Rj)(Rk)(Rl), L A' i'-(Ri)(Rj)(Rk)(Rl), LA' i"(Ri)(Rj)(Rk)(Rl) and L A' i'"-(Ri)(Rj)(Rk)(Rl);

[0301] wherein for L A' i-(Ri)(Rj)(Rk)(Rl), i is an integer from 1 to 16, and L A' i-(Ri)(Rj)(Rk)(Rl) is selected from the group consisting of L A' 1-(R2)(R2)(R1)(R1) to L A' 16-(R437)(R437(R437)(R437) and L A' 1-(R2)(R1)(R2)(R1) to L A' 16-(R437)(R437(R437)(R437);

[0302] wherein for L A' i'-(Ri)(Rj)(Rk)(Rl), i' is an integer from 17 to 23, and L A' i'-(Ri)(Rj)(Rk)(Rl) is selected from the group consisting of L A' 17-(R2)(R2)(R1)(R1) to L A' 23-(R437)(R437(R437)(R437) and L A' 17-(R2)(R1)(R1)(R2) to L A' 23-(R437)(R437(R437)(R437);

[0303] wherein for L A' i"(Ri)(Rj)(Rk)(Rl), i" is an integer from 24 to 32, and L A' i"(Ri)(Rj)(Rk)(Rl) is selected from the group consisting of L A' 24-(R2)(R1)(R1)(R1) to L A' 32-(R437)(R437(R437)(R437); and

[0304] wherein for L A' i'"-(Ri)(Rj)(Rk)(Rl), i'" is 33, and L A' i'"-(Ri)(Rj)(Rk)(Rl) is selected from the group consisting of L A' 33-(R2)(R1)(R1)(R1) to L A'33 - (R437)(R437(R437)(R437) and L A' 33 - (R1)(R1)(R1)(R2) to L A' 33 - (R437)(R437(R437)(R437) and

[0305] wherein L A'i - (Ri)(Rj)(Rk)(Rl), L A'i' - (Ri)(Rj)(Rk)(Rl), L A'i" - (Ri)(Rj)(Rk)(Rl) and L A'i"' - (Ri)(Rj)(Rk)(Rl) are each defined in List 7 below:

[0306]

[0307]

[0308]

[0309]

[0310] wherein L y is selected from L y n - (Rs)(Rt)(Ru)(Rv), wherein n is an integer from 1 to 68, and each of Rs, Rt, Ru, and Rv is independently selected from R1 to R437, and L y 1 - (R1)(R1)(R1)(R1) to L y 68 - (R437)(R437)(R437)(R437) are each defined in List 8 below:

[0311]

[0312]

[0313]

[0314]

[0315]

[0316]

[0317]

[0318] wherein R1 to R437 have the structures defined in List 9 below:

[0319]

[0320]

[0321]

[0322]

[0323]

[0324]

[0325]

[0326]

[0327]

[0328]

[0329]

[0330]

[0331]

[0332]

[0333]

[0334] In some embodiments, the compound is of the formula Pt(L A' i-(Ri)(Rj)(Rk)(Rl))(Ly))(L y n-(Rs)(Rt)(Ru)(Rv)), which is derived from Pt(L A' 1-(R2)(R2)(R1)(R1))(L y 1-(R1)(R1)(R1)(R1)) to Pt(L A' 16-(R437)(R437(R437)(R437))(L y 68-(R437)(R437)(R437)(R437)), or Pt(L A' 1-(R2)(R1)(R2)(R1))(L y 1-(R1)(R1)(R1)(R1)) to Pt(L A' 16-(R437)(R437(R437)(R437))(L y68-(R437)(R437)(R437)(R437)) of the formula Pt(L A'i' -(Ri)(Rj)(Rk)(Rl))(L y n-(Rs)(Rt)(Ru)(Rv)) of the formula Pt(L A' 17-(R2)(R2)(R1)(R1))(L y 1-(R1)(R1)(R1)(R1)) to Pt(L A' 23-(R437)(R437(R437)(R437))(L y 68-(R437)(R437)(R437)(R437)) of the formula Pt(L A' 17-(R2)(R1)(R1)(R2))(L y 1-(R1)(R1)(R1)(R1)) to Pt(L A' 23-(R437)(R437(R437)(R437))(L y 68-(R437)(R437)(R437)(R437)) of the formula Pt(L A'i" -(Ri)(Rj)(Rk)(Rl))(L y n-(Rs)(Rt)(Ru)(Rv)) of the formula Pt(L A' 24-(R2)(R1)(R1)(R1))(L y 1-(R1)(R1)(R1)(R1)) to Pt(L A' 32-(R437)(R437(R437)(R437))(L y 68-(R437)(R437)(R437)(R437)) of the formula Pt(L A'i"' -(Ri)(Rj)(Rk)(Rl))(L y n-(Rs)(Rt)(Ru)(Rv)) of the formula Pt(L A' 33-(R2)(R1)(R1)(R1))(L y 1-(R1)(R1)(R1)(R1)) to Pt(L A' 33-(R437)(R437(R437)(R437))(L y 68-(R437)(R437)(R437)(R437)) of the formula Pt(L A' 33-(R1)(R1)(R1)(R2))(L y 1-(R1)(R1)(R1)(R1)) to Pt(LA' 33-(R437)(R437(R437)(R437))(L y 68-(R437)(R437)(R437)(R437)) of the following compounds.

[0335] In some embodiments, the compound is selected from the group consisting of the structures of List 10:

[0336]

[0337]

[0338]

[0339]

[0340]

[0341]

[0342]

[0343]

[0344]

[0345]

[0346]

[0347] In some embodiments, the compound comprising the structure of Formula I described herein is partially or fully deuterated. In some embodiments, the compound is fully deuterated. In some embodiments, the first ligand L A of Formula I described herein can be at least 30% deuterated, at least 40% deuterated, at least 50% deuterated, at least 60% deuterated, at least 70% deuterated, at least 80% deuterated, at least 90% deuterated, at least 95% deuterated, at least 99% deuterated, or 100% deuterated. As used herein, the percentage deuterated has its ordinary meaning and includes the percentage of all possible hydrogen atoms (e.g., positions of hydrogen or deuterium) in the compound that are occupied by deuterium atoms. In some embodiments, the carbon atoms that make up the ring coordinated to the metal M are fully or partially deuterated. In some embodiments, the carbon atoms comprised by the polycyclic system coordinated to the metal M are fully or partially deuterated. In some embodiments, the substituents attached to the monocyclic or fused polycyclic system coordinated to the metal M are fully or partially deuterated.

[0348] In some embodiments, the compound of Formula I has an emission at room temperature with a full width at half maximum (FWHM) equal to or less than 50, 45, 40, 35, 30, 25, 20, 15, 10, or 5 nm. A narrower FWHM means better color purity for OLED display applications.

[0349] In some embodiments, the compound can be an emissive dopant. In some embodiments, the compound can produce emission via phosphorescence, fluorescence, thermally activated delayed fluorescence, triplet-triplet annihilation, or a combination of these methods. In some embodiments, the emissive dopant can be a racemic mixture, or can be enriched in one enantiomer. In some embodiments, the present compounds can have different stereoisomers, such as fac and mer. The present compounds are directed to individual isomers and mixtures of various isomers in any mixing ratio. In some embodiments, the compound can be homoleptic (each ligand is the same). In some embodiments, the compound can be heteroleptic (at least one ligand is different from the others).

[0350] When there is more than one ligand coordinating to the metal, in some embodiments, the ligands can all be the same. In some other embodiments, at least one ligand is different from the others. In some embodiments, each ligand can be different from all the other ligands. This also holds true in embodiments where the ligand coordinating to the metal can be linked to other ligands coordinating to the metal to form a tridentate, tetradentate, pentadentate, or hexadentate ligand. Thus, where the coordinating ligands are linked together, in some embodiments all the ligands can be the same, and in some other embodiments at least one of the linking ligands can be different from the other ligand(s).

[0351] In yet another aspect of the disclosure, a formulation comprising a novel compound disclosed herein is described. The formulation can include one or more components selected from the group consisting of solvents, emitters, hosts, hole injection materials, hole transport materials, electron blocking materials, hole blocking materials, and electron transport materials disclosed herein.

[0352] The present disclosure encompasses any chemical structure that comprises a novel compound of the present disclosure or a monovalent or multivalent variant thereof. In other words, the present compound or a monovalent or multivalent variant 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 supermolecules). As used herein, “monovalent variant of a compound” refers to the same moiety as the compound, but in which one hydrogen has been removed and replaced with a bond to the rest of the chemical structure. As used herein, “multivalent variant of a compound” refers to the same moiety as the compound, but in which more than one hydrogen has been removed and replaced with one or more bonds to the rest of the chemical structure. In the case of supramolecules, the present compound can also be incorporated into a supramolecular complex without a covalent bond. As used in this context, a description that structure A comprises part B means that structure A includes the structure of part B, which does not include the H or D atoms that can be attached to part B. This is because at least one of the H or D on a given moiety structure must be replaced with a substituent such that part B can be part of structure A, and after it becomes part of structure A, one or more of the H or D on the given moiety B structure can be further substituted.

[0353] C. OLEDs and devices of the present disclosure

[0354] In another aspect, the present disclosure also provides an OLED device comprising a first organic layer, the first organic layer containing a compound as disclosed in the above compound section of the present disclosure.

[0355] 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 compound comprising the structure of Formula I described herein.

[0356] 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 compound as described herein can be an emissive dopant or a non-emissive dopant.

[0357] In some embodiments, the organic layer can further comprise a host, wherein the host comprises at least one chemical group selected from the group consisting of a triphenylene, a carbazole, an indolocarbazole, a dithiophene, a dithiophene, a dithiophene, a 5λ 2- benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, 5,9-dioxa-13b-bora- naphtho[3,2,1-de]anthracene, azacyclohexaborane, oxaborabenzene, dihydroacridine, xanthene, dihydrobenzoazasiline, dibenzooxasiline, phenoxazine, phenoxathiine, phenothiazine, dihydrophenoxazine, fluorene, naphthalene, anthracene, phenanthrene, phenanthroline, benzochinoline, quinoline, isoquinoline, quinazoline, pyrimidine, pyrazine, pyridine, triazine, boranyl, silyl, azatriphenylene, azacarbazole, azaindolecarbazole, azadibenzothiophene, azadibenzofuran, azadibenzoselenophene, azacarbazolene-5λ 2 - benzo[d]benzo[4,5]imidazo[3,2-a]imidazole and azacarbazolene-5λ

[0358] In some embodiments, the main group can be selected from the group consisting of the structures in main group 1 below:

[0359]

[0360]

[0361]

[0362]

[0363]

[0364]

[0365]

[0366]

[0367]

[0368] wherein:

[0369] each of J1to J6is independently C or N;

[0370] L' is a direct bond or an organic linking group;

[0371] each Y AA , Y BB , Y CC , and Y DD is independently selected from the group consisting of no bond, a direct bond, O, S, Se, CRR', SiRR', GeRR', NR, BR, BRR';

[0372] R A' , R B' , R C' , R D' , R E' , R F' , and R G' each independently represents mono-substitution, up to the maximum substitution, or no substitution;

[0373] each R, R', R A' , R B' , R C' , R D' , R E' , R F' , and R G' is independently hydrogen or a substituent selected from the group consisting of general substituents as defined herein; any two substituents can be joined or fused to form a ring;

[0374] and, where possible, each unsubstituted aromatic carbon atom is optionally replaced with one or more N to form a nitrogen hetero substituted ring.

[0375] In some embodiments, at least one of J1to J3is N. In some embodiments, at least two of J1to J3are N. In some embodiments, all three of J1to J3are N. In some embodiments, each Y CC and Y DD is independently O, S, or SiRR', or more preferably O or S. In some embodiments, at least one unsubstituted aromatic carbon atom is replaced with N to form a nitrogen heterocycle.

[0376] In some embodiments, the host is selected from the group consisting of EG1-MG1-EG1to EG53-MG27-EG53having the formula EGa-MGb-EGc, or EG1-EG1to EG53-EG53having the formula EGa-EGcwhen MGb is absent, wherein 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 EG1to EG53are shown below:

[0377]

[0378]

[0379] The structures of MG1to MG27are shown below:

[0380]

[0381] In the MGb structures shown above, two bonding positions in the asymmetric structures MG10, MG11, MG12, MG13, MG14, MG17, MG24, and MG25 are labeled with numbers for identification purposes.

[0382] In some embodiments, the host can be any of itsaza-substituted variants, its fully or partially deuterated variants, and combinations thereof. In some embodiments, the host is of the formula EGa-MGb-Egc and is selected from the group consisting of h1 to h112 as defined in the following Host Group 2 list, wherein each of MGb, EGa, and Egc is defined as follows:

[0383]

[0384] In the above table, the EGa and EGc structures bonded to one of the asymmetric structures MG10, MG11, MG12, MG13, MG14, MG17, MG24, and MG25 are labeled with a number prefix that identifies their bonding position in the MGb structure.

[0385] In some embodiments, the organic layer can further comprise a host, wherein the host comprises a metal complex.

[0386] In some embodiments, the emissive layer can include two hosts: a first host and a second host. In some embodiments, the first host is a hole transport host and the second host is an electron transport host. In some embodiments, the first host is a hole transport host and the second host is a bipolar host. In some embodiments, the first host is an electron transport 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 emissive layer can include a third host. In some embodiments, the third host is selected from the group consisting of an insulating host (wide band gap host), a hole transport host, and an electron transport host. In some embodiments, the third host forms an exciplex with one of the first host and the second host or with both the first host and the second host. In some embodiments, the emissive layer can include a fourth host. In some embodiments, the fourth host is selected from the group consisting of an insulating host (wide band gap host), a hole transport host, and an electron transport 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 transport host has a LUMO 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 transport host has a HOMO higher than -5.6 eV, higher than -5.5 eV, higher than -5.4 eV, or higher than -5.35 eV. HOMO and LUMO values can be determined using solution electrochemistry. Solution cyclic voltammetry and differential pulse voltammetry can be performed using a CH Instruments model 6201B potentiostat, using anhydrous dimethylformamide (DMF) solvent and tetrabutylammonium hexafluorophosphate as a supporting electrolyte. Glassy carbon, platinum wire, and silver wire are used as the working electrode, the counter electrode, and the reference electrode, respectively. The electrochemical potential can be referenced to the internal ferrocene-ferrocenium salt redox couple (Fc / Fc+) by the peak potential difference measured by differential pulse voltammetry.According to the literature ((a) Fink R.; Heischkel Y.; Thelakkat M.; Schmidt H.-W., Chem. Mater. 1998, 10, 3620-3625; (b) Pommerehne J.; Vestweber H.; Guss W.; Mahrt R.F.; Bassler H.; Porsch M.; Daub, J. Adv. Mater. 1995, 7, 551), the corresponding highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energies are determined by the cationic and anionic redox potentials relative to the ferrocenium reference (4.8 eV vs. vacuum).

[0387] In some embodiments, a compound as described herein can be a sensitizer or a component of a sensitizer; wherein the device can further comprise an acceptor that receives energy from the sensitizer. In some embodiments, the acceptor is an emitter in the device. In some embodiments, the acceptor can be a fluorescent material. In some embodiments, a compound described herein can be used as a phosphorescent sensitizer in an OLED, wherein one or more layers in the OLED contain an acceptor in the form of one or more non-delayed fluorescent and / or delayed fluorescent materials. In some embodiments, a compound described herein can be used as one component of an exciplex used as a sensitizer. As a phosphorescent sensitizer, the compound must be able to transfer energy to an acceptor and the acceptor will emit energy or further transfer energy to a final emitter. The acceptor concentration can range from 0.001% to 99.9%. The acceptor can be in the same layer as the phosphorescent sensitizer or in one or more different layers. In some embodiments, the acceptor is a thermally activated delayed fluorescence (TADF) material. In some embodiments, the acceptor is a non-delayed fluorescent material. In some embodiments, emission can be produced by any or all of the sensitizer, the acceptor, and the final emitter. In some embodiments, the acceptor has an emission at room temperature with a full width at half maximum (FWHM) equal to or less than 50, 45, 40, 35, 30, 25, 20, 15, 10, or 5 nm. A narrower FWHM means that the OLED shows better color purity for the application.

[0388] As used herein, phosphorescence generally refers to the emission of a photon upon a change in the electron spin quantum number, i.e., the initial and final states of the emission have different electron spin quantum numbers, such as from a T1 to an S0 state. Most of the Ir and Pt complexes currently used in OLEDs are phosphorescent emitters. In some embodiments, if an excited state complex formation involves a triplet emitter, such an excited state complex can also emit phosphorescence. On the other hand, a fluorescent emitter generally refers to the emission of a photon upon no change in the electron spin quantum number, such as from an S1 to an S0 state, or from a D1 to a D0 state. A fluorescent emitter can be a delayed fluorescent or non-delayed fluorescent emitter. Depending on the spin state, a fluorescent emitter can be a singlet emitter or a triplet emitter or other multiplet emitter. It is believed that the internal quantum efficiency (IQE) of a fluorescent OLED can exceed the 25% spin-statistics limit with delayed fluorescence. There are two types of delayed fluorescence, i.e., P-type and E-type delayed fluorescence. P-type delayed fluorescence results 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 a triplet and a singlet excited state. Thermal energy can activate the triplet to transition back to a singlet. This type of delayed fluorescence is also referred to as TADF. E-type delayed fluorescence characteristics can be found in an excited state complex system or a single compound. Without being bound by theory, it is believed that a compound or an excited state complex with a small singlet-triplet energy gap (ΔEST) of less than or equal to 400, 350, 300, 250, 200, 150, 100, or 50 meV is required for TADF emission. There are two main types of TADF emitters, one is called donor-acceptor type TADF, and the other is called multi-resonance (MR) TADF. Typically, a single compound donor-acceptor TADF compound is constructed by linking an electron donor moiety (such as an amino or carbazole derivative) and an electron acceptor moiety (such as an N-containing six-membered aromatic ring or a cyano-substituted aromatic ring). A donor-acceptor excited state complex can be formed between a hole transporting compound and an electron transporting compound. Examples of MR-TADF materials include highly conjugated fused ring systems. In some embodiments, the MR-TADF materials comprise boron, carbon, and nitrogen atoms. Such materials can also comprise other atoms, such as oxygen. In some embodiments, the reverse intersystem crossing time from T1 to S1 for the delayed fluorescence emission is less than or equal to 10 microseconds at 293 K. In some embodiments, such time can be greater than 10 microseconds and less than 100 microseconds. S-T ) of less than or equal to 400, 350, 300, 250, 200, 150, 100, or 50 meV. There are two main types of TADF emitters, one is called donor-acceptor type TADF, and the other is called multi-resonance (MR) TADF. Typically, a single compound donor-acceptor TADF compound is constructed by linking an electron donor moiety (such as an amino or carbazole derivative) and an electron acceptor moiety (such as an N-containing six-membered aromatic ring or a cyano-substituted aromatic ring). A donor-acceptor excited state complex can be formed between a hole transporting compound and an electron transporting compound. Examples of MR-TADF materials include highly conjugated fused ring systems. In some embodiments, the MR-TADF materials comprise boron, carbon, and nitrogen atoms. Such materials can also comprise other atoms, such as oxygen. In some embodiments, the reverse intersystem crossing time from T1 to S1 for the delayed fluorescence emission is less than or equal to 10 microseconds at 293 K. In some embodiments, such time can be greater than 10 microseconds and less than 100 microseconds.

[0389] In some embodiments, the OLED can comprise an additional compound selected from the group consisting of a non-delayed fluorescent material, a delayed fluorescent material, a phosphorescent material, and combinations thereof.

[0390] In some embodiments, the inventive compounds described herein are phosphorescent materials.

[0391] In some embodiments, the phosphorescent material is an emitter that emits light within the OLED. In some embodiments, the phosphorescent material does not emit light within the OLED. In some embodiments, the phosphorescent material energy 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 component of a sensitizer, and the OLED further comprises an acceptor. In some embodiments, the phosphorescent material forms an exciplex with another material (e.g., host material, emitter material) within the OLED.

[0392] In some embodiments, the non-delayed fluorescent material or delayed fluorescent material is an emitter that emits light within the OLED. In some embodiments, the non-delayed fluorescent material or delayed fluorescent material does not emit light within the OLED. In some embodiments, the non-delayed fluorescent material or delayed fluorescent material energy transfers its excited state to another material within the OLED. In some embodiments, the non-delayed fluorescent material or delayed fluorescent material participates in charge transport within the OLED. In some embodiments, the non-delayed fluorescent material or delayed fluorescent material is an acceptor, and the OLED further comprises a sensitizer.

[0393] 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 known as 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 comprises at least one chemical group selected from the group consisting of aryl-amine, aryloxy, arylthio, triphenylene, carbazole, indolocarbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, 5λ 2 benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, 5,9-dioxa-13b-borafluorene[3,2,1-de]anthracene, 5λ 2 ,9λ 2 -diaza-13b-borafluorene[2,3,4-de]anthracene, 5-oxa-9λ 2-aza-13b-boronazonaphtho[3,2,1-de]anthracene, azacyclohexylborane, oxaborane, dihydroacridine, oxanthracene, dihydrobenzoazasilane, dibenzooxasilane, phenoxazine, phenoxthiazine, dihydrophenoxazine, fluorene, naphthalene, anthracene, phenanthrene, phenanthroline, benzoquinoline, quinoline, isoquinoline, quinazoline, pyrimidine, pyrazine, pyridine, triazine, borane, amino, silane, their aza variants and combinations thereof. In some embodiments, the non-delayed fluorescent material or the delayed fluorescent material comprises tri(aryl / heteroaryl)borane, wherein one or more pairs of substituents from the aryl / heteroaryl group are bonded to form a ring. In some embodiments, the fluorescent material comprises at least one chemical group selected from the group consisting of: naphthalene, anthracene, phenanthrene, fluorene, pyrene, Perylene and azurite.

[0394] In another aspect, the OLED of this disclosure may further include an emitting region containing a compound or formulation of a compound as disclosed in the foregoing compound portion of this disclosure. In some embodiments, the emitting region may contain a compound or a formulation of a compound comprising the structure of Formula I described herein. In some embodiments, the emitting region comprises one or more organic layers, wherein at least one of the one or more organic layers has a minimum thickness selected from the group consisting of: 350, 400, 450, 500, 550, 600, 650 and In some embodiments, at least one of the one or more organic layers is formed by an emission system having a figure of merit (FOM) equal to or greater than a value selected from the group consisting of: 2.50, 2.55, 2.60, 2.65, 2.70, 2.75, 2.80, 2.85, 2.90, 2.95, 3.00, 5.00, 10.0, 15.0, and 20.0. 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 formulation of a compound as disclosed in Parts A and D of this disclosure.

[0395] In some embodiments, the OLEDs or emissive regions disclosed herein comprising a compound of the application can be incorporated into a full color pixel arrangement of a device. A full color pixel arrangement of such a device comprises at least one pixel, wherein the at least one pixel comprises a first sub-pixel and a second sub-pixel. The first sub-pixel comprises a first OLED comprising a first emissive region. The second sub-pixel comprises a second OLED comprising a second emissive region. In some embodiments, the first and / or second OLEDs, the first and / or second emissive regions can be the same or different and each can independently have various device features and various embodiments of a compound of the application included therein, as well as various combinations and subcombinations of various device features and various embodiments of a compound of the application included therein, as disclosed herein.

[0396] In some embodiments, the first emissive region is configured to emit light having a peak wavelength λ max1 ; the second emissive region is configured to emit light having a peak wavelength λ max2 . In some embodiments, the difference between peak wavelengths λ max1 and λ max2 is at least 4 nm but within the same color. For example, the light described above as light of a light blue color and a dark blue color. In some embodiments, the first emissive region is configured to emit light having a peak wavelength λ max1 in one region of the visible spectrum of 400-500 nm, 500-600 nm, 600-700 nm; and the second emissive region is configured to emit light having a peak wavelength λ max2 in one of the remaining regions of the visible spectrum of 400-500 nm, 500-600 nm, 600-700 nm. In some embodiments, the first emissive region comprises (if more than one) a first number of emissive layers deposited on one another; and the second emissive region comprises (if more than one) a second number of emissive layers deposited on one another; and the first number is different from the second number. In some embodiments, both the first emissive region and the second emissive region comprise a phosphorescent material, which can be the same or different. In some embodiments, the first emissive region comprises a phosphorescent material, while the second emissive region comprises a fluorescent material. In some embodiments, both the first emissive region and the second emissive region comprise a fluorescent material, which can be the same or different.

[0397] In some embodiments, at least one pixel of the OLED or emissive region comprises a total of N sub-pixels; wherein the N sub-pixels comprise a first sub-pixel and a second sub-pixel; wherein each of the N sub-pixels comprises an emissive region; wherein the total number of emissive regions within the at least one pixel is equal to or less than N-1. In some embodiments, the second emissive region is identical to the first emissive region; and each sub-pixel of the at least one pixel comprises one emissive region identical to the first emissive region. In some embodiments, a full color pixel arrangement can have a plurality of pixels comprising a first pixel region and a second pixel region; wherein at least one display characteristic in the first pixel region is different from a corresponding display characteristic of the second pixel region, and wherein the at least one display characteristic is selected from the group consisting of: resolution, cavity mode, color, out-coupling, and color filter.

[0398] In some embodiments, the OLED is a stacked OLED comprising one or more charge generation layers (CGLs). In some embodiments, the OLED comprises a first electrode, a first emissive region disposed over the first electrode, a first CGL disposed over the first emissive region, a second emissive region disposed over the first CGL, and a second electrode disposed over the second emissive region. In some embodiments, the first emissive region and / or the second emissive region can have various device features as described above for the pixelated device. In some embodiments, the stacked OLED is configured to emit white. In some embodiments, one or more of the emissive regions in the pixelated OLED or stacked OLED comprise a sensitizer and an acceptor having various sensitizing device features and various embodiments of the inventive compounds disclosed herein. For example, the first emissive region is comprised in a sensitizing device, while the second emissive region is not comprised in a sensitizing device; in some cases, both the first emissive region and the second emissive region are comprised in a sensitizing device.

[0399] In some embodiments, the OLED can emit light from the plasmonic mode with at least 1%, 5%, 10%, 30%, 50%, 70%, 80%, 90%, 95%, 99%, or 100%. In some embodiments, at least one of the anode, the cathode, or a new layer disposed above the organic emissive layer acts as an enhancement layer. The enhancement layer includes a plasmonic material that exhibits surface plasmon resonance, which non-radiatively couples to the emitter material and transfers excitation state energy from the emitter material to non-radiative modes of the surface plasmon polaritons. In some embodiments, the enhancement layer is disposed at a distance from the organic emissive layer that does not exceed a threshold distance, where the emitter material has a total non-radiative decay rate constant and a total radiative decay rate constant due to the presence of the enhancement layer. The threshold distance is where the total non-radiative decay rate constant equals the total radiative decay rate constant. Another threshold distance is where the total radiative decay rate constant divided by the sum of the total non-radiative decay rate constant and the total radiative decay rate constant equals the photoluminescence quantum yield of the emissive material in the absence of the enhancement layer.

[0400] In some embodiments, the OLED further includes an out-coupling layer. In some embodiments, the out-coupling layer is disposed above the enhancement layer on a side opposite the organic emissive layer. The out-coupling layer scatters energy from the surface plasmon polaritons. In some embodiments, this energy is scattered as photons into free space. In other embodiments, the energy is scattered from the surface plasmonic mode of the device into other modes, 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 out-coupling layer. Examples of intervening layers can be dielectric materials, including organic, inorganic, perovskite, oxide, and can include stacks and / or mixtures of these materials.

[0401] The enhancement layer changes the effective properties of the medium in which the emitter material resides, resulting in any or all of the following: reduced emissivity, altered emission line shape, emission intensity variation with angle, altered emitter material stability, altered OLED efficiency, and reduced OLED device roll-off efficiency. Placing an enhancement layer on the cathode side, the anode side, or both, or placing the 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 mentioned herein and illustrated in the various OLED examples shown in the figures, the OLEDs according to the present disclosure can also include any other functional layers commonly found in OLEDs.

[0402] In some embodiments, the enhancement layer can comprise a plasmonic material, an optically active supermaterial, or a hyperbolic supermaterial. In some embodiments, the plasmonic material comprises at least one metal. In such embodiments, the metal can comprise 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 disposed as a planar layer. In other embodiments, the enhancement layer has periodically, quasi-periodically, or randomly arranged wavelength-sized features, or has periodically, quasi-periodically, or randomly arranged sub-wavelength-sized features.

[0403] In some embodiments, the outcoupling layer has periodically, quasi-periodically, or randomly arranged wavelength-sized features or sub-wavelength-sized features. In some embodiments, the outcoupling layer can be composed of a plurality of nanoparticles. In some embodiments, the outcoupling layer is composed of a plurality of nanoparticles disposed above a material. In these embodiments, the outcoupling layer can be tuned by at least one of changing the size of the plurality of nanoparticles, changing the shape of the plurality of nanoparticles, changing the material of the plurality of nanoparticles, tuning the thickness of the material, changing the refractive index of the material, adding an additional layer disposed on the plurality of nanoparticles, changing the thickness of the enhancement layer, or changing the material of the enhancement layer. The plurality of nanoparticles of the device can be formed of at least one of a metal, a dielectric material, a semiconductor material, an alloy of metals, a mixture of dielectric materials, a stack or a hierarchy 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, where the metal is selected from the group consisting of Ag, Al, Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ru, Pd, In, Bi, and Ca, alloys or mixtures of these materials, and stacks of these materials. In some embodiments, the outcoupling layer is formed by photolithography.

[0404] In some embodiments of the plasmonic device, the emitter and / or host compound used in the emission layer has a vertical dipole ratio (VDR) of 0.33 or greater. In some such embodiments, the emitter and / or host compound has a VDR of 0.40, 0.50, 0.60, 0.70, or greater.

[0405] 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 formulation of compounds as disclosed in the above compound section of the present disclosure.

[0406] In some embodiments, the consumer product comprises an OLED having an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer can comprise [copy of claim 1].

[0407] Generally, an OLED comprises at least one organic layer disposed between and electrically connected to an anode and a cathode. When a potential is applied across the layers, holes are injected from the anode through the organic layer(s) and electrons are injected from the cathode through the organic layer(s). The holes and electrons each migrate toward the oppositely charged electrode. When an electron and hole localize on the same molecule, an "exciton," which is a localized electron-hole pair having an excited energy state, is formed. When the exciton relaxes, it releases energy that can take the form of light. In some cases, the exciton can localize at an excimer or an exciplex. Non-radiative mechanisms, such as thermal relaxation, can also occur, but are generally considered undesirable.

[0408] Figure 1 An organic light emitting device 100 is shown. The figures are not necessarily drawn to scale. The device 100 can include a substrate 110, an anode 115, a hole injection layer (HIL) 120, a hole transport layer (HTL) 125, an electron blocking layer (EBL) 130, an emission layer (EML) 135, a hole blocking layer (HBL) 140, an electron transport layer (ETL) 145, an electron injection layer (EIL) 150, a protective layer 155, a cathode 160, and a blocking layer 170. The cathode 160 is a composite cathode having a first conductive layer 162 and a second conductive layer 164. The device 100 can be fabricated by sequentially depositing the layers. The properties and functions of these various layers, as well as example materials, are described in more detail in US 7,279,704, columns 6-10, which is incorporated by reference.

[0409] More examples of each of these layers can be found. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. Patent No. 5,844,363, incorporated by reference in its entirety. An example of a p-doped hole transport layer is m-MTDATA doped with F4-TCNQ in a 50:1 molar ratio, as disclosed in U.S. Patent Application Publication No. 2003 / 0230980, incorporated by reference in its entirety. Examples of light emitting and host materials are disclosed in U.S. Patent No. 6,303,238 to Thompson et al., incorporated by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li in a 1:1 molar ratio, as disclosed in U.S. Patent Application Publication No. 2003 / 0230980, incorporated by reference in its entirety. U.S. Patent Nos. 5,703,436 and 5,707,745, incorporated by reference in their entirety, disclose examples of cathodes including composite cathodes with a thin layer of metal (such as Mg:Ag) overlying a transparent, conductive, sputter-deposited ITO layer. The theory and use of barrier layers are described in more detail in U.S. Patent No. 6,097,147 and U.S. Patent Application Publication No. 2003 / 0230980, incorporated by reference in their entirety. Examples of injection layers are provided in U.S. Patent Application Publication No. 2004 / 0174116, incorporated by reference in its entirety. Descriptions of protective layers can be found in U.S. Patent Application Publication No. 2004 / 0174116, incorporated by reference in its entirety.

[0410] Figure 2 An inverted OLED 200 is shown. The device includes a substrate 210, a cathode 215, an emissive layer 220, a hole transport layer 225, and an anode 230. Device 200 can be fabricated by depositing the layers sequentially, as described for device 100. Because most common OLED configurations have a cathode disposed over the anode, and device 200 has a cathode 215 disposed under the anode 230, device 200 can be referred to as an "inverted" OLED. Similar materials as those described for device 100 can be used in the corresponding layers of device 200. Figure 2 One example of how some layers can be omitted from the structure of device 100 is provided.

[0411] Figure 1 and 2The simple layered structure illustrated in the middle is provided by way of non-limiting example, and it is understood that embodiments of the present disclosure can be used in conjunction with a variety of other structures. The particular materials and structures described are exemplary in nature and other materials and structures can be used. Functional OLEDs can be obtained by combining the various layers described in different ways, or the layers can be omitted entirely. Other layers not specifically described can also be included. Materials other than those specifically described can be employed. As an example, the OLED can be described as having a single layer, or a mixture of materials, as opposed to a plurality of sub-layers, although the various sub-layers can be combined into a single layer. The names given to the various layers do not limit the scope of the invention. For example, in device 200, the hole transport layer 225 transports holes and injects holes into the emission layer 220, and can be described as a hole transport layer or a hole injection layer. In one embodiment, an OLED can be described as having an "organic layer" disposed between a cathode and an anode. This organic layer can comprise a single layer, or can further comprise multiple layers of different organic materials as described, for example, with respect to Figure 1 and 2 the different organic materials described, for example, with respect to

[0412] Structures and materials other than those specifically described can be used. For example, OLEDs including polymeric materials can be used, as described in, for example, U.S. Patent No. 5,247,190, by Friend et al., incorporated by reference in its entirety. By way of another example, OLEDs having a single organic layer can be used. OLEDs can be stacked, as described in U.S. Patent No. 5,707,745, by Forrest et al., incorporated by reference in its entirety. OLED structures can deviate from the simple layered structure illustrated in the middle of Figure 1 and 2 For example, a substrate can include an angled reflective surface to improve out-coupling, such as a table structure described in U.S. Patent No. 6,091,195, by Forrest et al., and / or a concave point structure described in U.S. Patent No. 5,834,893, by Bulovic et al., incorporated by reference in their entirety.

[0413] Unless otherwise described, any of the layers of the various embodiments can be deposited by any suitable method. For organic layers, preferred methods include thermal evaporation, ink-jet (as described in U.S. Pat. Nos. 6,013,982 and 6,087,196, which are incorporated by reference in their entireties), organic vapor phase deposition (OVPD) as described in U.S. Pat. No. 6,337,102 to Fifer et al., which is incorporated by reference in its entirety, and deposition by organic vapor jet printing (OVJP, also referred to as organic vapor jet deposition (OVJD)) as described in U.S. Pat. No. 7,431,968, which is incorporated by reference in its entirety. Other suitable deposition methods include spin coating and other solution based processes. Solution based processes are preferably conducted in nitrogen or inert atmospheres. For other layers, preferred methods include thermal evaporation, sputtering, chemical vapor deposition, atomic layer deposition, and e-beam deposition. Preferred patterning methods include deposition through a mask, photolithography, and cold welding (as described in U.S. Pat. Nos. 6,294,398 and 6,468,819, which are incorporated by reference in their entireties) and patterning associated with, for example, ink-jet and organic vapor jet printing (OVJP) deposition methods. Other methods can also be used. The materials to be deposited can be modified in order to adapt them to the particular deposition method. For example, substituents can be used in small molecules to enhance their solution processability. Substituents such as alkyl and aryl groups, branched or unbranched, and preferably containing at least 3 carbons, can be used in small molecules to enhance their solution processability. Substituents with 20 or more carbons can be used, and from 3 to 20 carbons are a preferred range. Materials with asymmetric structures can have better solution processability than those with symmetric structures, because they can have lower recrystallization tendency. Dendrimer substituents can be used to enhance solution processability of small molecules.

[0414] Devices fabricated in accordance with embodiments of the disclosure can further optionally include a barrier layer. One use of a barrier layer is to protect the electrodes and organic layer from the deleterious effects of exposure to an environment including oxygen, moisture, and / or gases, etc. The barrier layer can be deposited on the substrate, electrode(s), or both, and can be deposited between some or all of the electrodes. A barrier layer can be deposited on the entire surface of the device, or only on portions of the surface. A barrier layer can be deposited all around the perimeter of the device, or only on a partial perimeter. The barrier layer can be deposited on the substrate, on the electrode(s), or on both the substrate and the electrode(s). A barrier layer can be deposited on any other portion of the device including the edges. The barrier layer can be deposited using any appropriate technique. For example, the deposition can be accomplished using chemical vapor deposition, thermal evaporation, sputtering, and / or physical vapor deposition, among other techniques. The deposition can be accomplished using any appropriate material or combination of materials. The barrier layer can comprise a single layer or multiple layers. The barrier layer can be formed of an inorganic compound or an organic compound, or both. Preferred barrier layers comprise multiple alternating layers of polymeric and non-polymeric materials, organic and inorganic materials, or mixtures of polymeric and non-polymeric materials, one example of which is described in U.S. Patent No. 7,968,146, PCT Patent Application Nos. PCT / US2007 / 023098 and PCT / US2009 / 042829, which are incorporated by reference in their entirety.

[0415] Devices made in accordance with embodiments of the disclosure can be incorporated into a wide variety of electronic assembly modules (or units) that can be incorporated into a wide variety of electronic products or intermediate assemblies. Examples of the electronic products or intermediate assemblies include display screens, lighting devices (such as discrete light source devices or lighting panels), etc. that can be utilized by end- user product manufacturers. The electronic assembly modules can optionally include driving electronics and / or power supplies. Devices made in accordance with embodiments of the disclosure can be incorporated into a wide variety of consumer products that have one or more electronic assembly modules (or units) incorporated therein. A consumer product is disclosed that includes an OLED that includes a compound of the disclosure in an organic layer in the OLED. The consumer product should include any kind of product that includes one or more of one or more light sources and / or some type of visual display. Some examples of the consumer product include flat panel displays, curved displays, computer monitors, medical monitors, televisions, billboards, lights for interior or exterior illumination and / or signaling, heads-up displays, fully transparent or partially transparent displays, flexible displays, rollable displays, foldable displays, stretchable displays, laser printers, telephones, cellular phones, tablet computers, phablets, personal digital assistants (PDAs), wearable devices, laptop computers, digital cameras, video cameras, viewfinders, micro-displays (displays less than 2 inches in diagonal), 3-D displays, virtual reality or augmented reality displays, vehicles, video walls containing multiple displays tiled together, theater or stadium screens, light therapy devices, and signs. Devices made in accordance with the disclosure can be controlled using a variety of control mechanisms, including passive matrix and active matrix. It is intended that many of the devices be used in temperature ranges comfortable for humans, such as 18 °C to 30 °C, and more preferably at room temperature (20-25 °C), but can be used outside this temperature range (e.g., -40 °C to +80 °C).

[0416] Further details regarding OLEDs and the definitions described above can be found in U.S. Patent No. 7,279,704, which is incorporated herein by reference in its entirety.

[0417] The materials and structures described herein can be applied to devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors can employ the materials and structures. More generally, organic devices such as organic transistors can employ the materials and structures.

[0418] In some embodiments, the OLED has one or more features selected from the group consisting of: flexible, rollable, foldable, stretchable, and bendable. In some embodiments, the OLED is transparent or semi-transparent. In some embodiments, the OLED further comprises a layer comprising carbon nanotubes. In some embodiments, the OLED further comprises one or more quantum dots. Such quantum dots can be in the emissive layer, or in other functional layers, such as a down-conversion layer.

[0419] In some embodiments, the OLED comprises an RGB pixel arrangement or a white plus color filter pixel arrangement. In some embodiments, the OLED is a mobile device, a handheld device, or a wearable device. In some embodiments, the OLED is a display panel with a diagonal less than 10 inches or an area less than 50 square inches. In some embodiments, the OLED is a display panel with a diagonal of at least 10 inches or an area of at least 50 square inches. In some embodiments, the OLED is an illumination panel.

[0420] Other materials used in OLEDs

[0421] The materials described herein are useful as various examples of specific layers that can be used in OLEDs. They can also be used in combination with a wide variety of other materials present in devices. For example, the emissive dopants disclosed herein can be used by themselves as the emissive dopant in the EML, or in combination with a wide variety of other emitters, hosts, transport layers, blocking layers, injection layers, electrodes, and other layers that can be present. The materials described or referred to below are non-limiting examples of materials that can be used in combination with the compounds and devices disclosed herein, and one of skill in the art can readily consult the literature to identify other materials that can be used in combination.

[0422] a) Conductive dopants:

[0423] Charge transport layers can be doped with conductive dopants to substantially change their charge carrier density, which in turn will change their conductivity. The conductivity is increased by the creation of charge carriers in the matrix material, and depending on the type of dopant, a shift of the Fermi level of a semiconductor can also be achieved. Hole transport layers can be doped with p-type conductive dopants, and n-type conductive dopants are used in electron transport layers. In some embodiments, the conductive dopants comprise at least one chemical moiety selected from the group consisting of: cyano groups, fluorinated aryl or heteroaryl groups, fluorinated alkyl or cycloalkyl groups, alkylene groups, heteroaryl groups, amides, benzo dithiophenes, and highly conjugated heteroaryl groups extended by acyclic double bonds.

[0424] b) HIL / HTL:

[0425] The hole injection / transport material used in the present disclosure is not particularly limited, and any compound can be used as long as the compound is generally used as a hole injection / transport material. Examples of the material include, but are not limited to, phthalocyanine or porphyrin derivatives; aromatic amine derivatives; indolocarbazole derivatives; fluorocarbon-containing polymers; polymers with conductive dopants; conductive polymers such as PEDOT / PSS; self-assembled monomers derived from compounds such as phosphonic acid and silane derivatives; metal oxide derivatives such as MoO x ; p-type semiconductive organic compounds such as 1,4,5,8,9,12-hexaazatriphenylhexacarbonitrile; metal complexes; and cross-linkable compounds.

[0426] Examples of the aromatic amine derivative used for the HIL or HTL include, but are not limited to, the following general structures:

[0427]

[0428] Ar 1 to each of Ar 9 is selected from the group consisting of aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, terphenyl, triphenylene, naphthalene, anthracene, azulene, phenanthrene, fluorene, pyrene, pyranthrene, and azulene; aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolo-dipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indooxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthpyridine, phtalazine, pteridine, xanthene, acridine, phenoxazine, phenothiazine, phenoxazine, benzofuropyridine, furopyridine, benzothiophuropyridine, thio-pyridine, benzoselenophuropyridine, and selenophene-dipyridine; and the group consisting of 2 to 10 cyclic structural units which are the same type or different types of radicals selected from aromatic hydrocarbon ring radicals and aromatic heterocyclic ring radicals and are bonded to each other directly or via at least one of oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms, phosphorus atoms, boron atoms, chain structural units, and aliphatic ring radicals. Ar 1 to each of Ar 9 may be unsubstituted or can be substituted with the general substituent as described above, any two substituents can be joined or fused into a ring.

[0429] In some embodiments, each Ar 1 to Ar 9 independently comprises a moiety selected from the group consisting of

[0430]

[0431] wherein k is an integer from 1 to 20; X 101 to X 108 is C or N; Z 101 is C, N, O, or S.

[0432] Examples of metal complexes used in the HIL or HTL include, but are not limited to, the following general formula:

[0433]

[0434] wherein Met is a metal having an atomic weight greater than 40; (Y 101 -Y 102 ) is a bidentate ligand, Y 101 and Y 102 are coordinating atoms independently selected from C, N, O, P, and S; L 101 is another ligand; k' is an integer value from 1 to the maximum number of ligands that can be attached to the metal; and k' + k" is the maximum number of ligands that can be attached to the metal.

[0435] In some embodiments, (Y 101 -Y 102 ) is a 2-phenylpyridine or 2-phenylimidazole derivative. In some embodiments, (Y 101 -Y 102 ) is a carbene ligand. In some embodiments, Met is selected from Ir, Pt, Pd, Os, Cu, and Zn. In some embodiments, the metal complex has a minimum oxidation potential in solution that is less than about 0.6 V smaller than the Fc + / Fc couple.

[0436] In some embodiments, the HIL / HTL material is selected from the group consisting of phthalocyanine and porphyrin compounds, starburst triarylamines, CF x fluorocarbon polymers, conductive polymers (e.g., PEDOT:PSS, polyaniline, polythiophene), phosphonic acid and silane SAMs, triarylamine or polythiophene polymers containing conductive dopants, organic compounds containing conductive inorganic compounds such as molybdenum oxide and tungsten oxide, n-type semiconductive organic complexes, metal organic metal complexes, cross-linkable compounds, polymeric and copolymeric polymers based on polythiophene, triarylamines, triarylamine containing spirofluorene core, arylamine carbazole compounds, triarylamine containing (di)benzothiophene / (di)benzofuran, indolocarbazole, isoindole compounds, and metal carbene complexes.

[0437] c) EBL:

[0438] An electron blocking layer (EBL) can be used to reduce the number of electrons and / or excitons leaving the emissive layer. The presence of such a blocking layer in a device can result in a device that has a generally higher efficiency and / or a longer lifetime compared to a similar device lacking the blocking layer. Further, the blocking layer can be used to confine emission to a desired area or areas of the 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 of the 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 aryl amine group. In some embodiments, the compound used in the EBL has a HOMO energy level shallower than the HOMO energy level of one or more of the hosts in the EML. In some embodiments, the compound used in the EBL contains the same molecule or the same functional group as used in one of the hosts described below.

[0439] d) Host:

[0440] The light-emitting layer of the organic EL device of the present disclosure preferably contains at least a light-emitting material as a dopant, and a host material. Examples of the host material are not particularly limited, and any metal complex or organic compound can be used as long as the host does not completely quench the emission of the dopant.

[0441] Examples of the metal complex used as the host preferably have the following general formula:

[0442]

[0443] wherein Met is a metal; (Y 103 -Y 104 ) is a bidentate ligand, Y 103 and Y 104 are coordination atoms of Y 101 and Y 103 are independently selected from C, N, O, P, and S; L 104 is another ligand; k' is an integer value from 1 to the maximum number of ligands that can be attached to the metal; and k' + k" is the maximum number of ligands that can be attached to the metal.

[0444] In some embodiments, the metal complex is:

[0445]

[0446] wherein (O-N) is a bidentate ligand having a metal coordinated to O and N atoms.

[0447] In some embodiments, Met is selected from Ir and Pt. In another embodiment, (Y 103 -Y 104 ) is a carbene ligand.

[0448] In some embodiments, the host compound contains at least one from the following groups selected from the group consisting of aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, rea, phenanthrene, fluorene, pyrene, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolo-dipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indooxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthridine, phtalazine, pteridine, xanthene, acridine, phenoxazine, phenothiazine, phenoxazine, azadibenzothiophene, azadibenzofuran, azadibenzoselenophene, azacarbazole, azaindolocarbazole, azatriphenylene, azatetraphenylene, 5λ 2 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 which are groups of the same type or different types selected from aromatic hydrocarbon ring groups and aromatic heterocyclic ring groups and are bonded to each other directly or via at least one of oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms, phosphorus atoms, boron atoms, chain structural units, and aliphatic ring groups. Each option within each group can be unsubstituted or can be substituted with the general substituents as described herein or can be further fused.

[0449] In some embodiments, the host compound comprises at least one from the group consisting of moieties selected from the group consisting of:

[0450]

[0451]

[0452] wherein k is an integer from 0 to 20 or 1 to 20. X 101 to X 108 is independently selected from C or N. Z 101 and Z 102 is independently selected from C, N, O, or S.

[0453] In some embodiments, the host material is selected from the group consisting of arylcarbazoles, metal 8-hydroxyquinolinate (e.g., alq3, balq), metal phenoxybenzothiazole compounds, conjugated oligomers and polymers (e.g., polyfluorenes), aromatic fused rings, zinc complexes, based on compounds, aryltriphenylenyl compounds, polyfused heteroaryl compounds, donor-acceptor type molecules, dibenzofuran / dibenzothiophene compounds, polymers (e.g., PVK), spirofluorene compounds, spirofluorene-carbazole compounds, indolocarbazole, 5-membered ring electron-deficient heterocycles (e.g., triazole, oxadiazole), tetraphenyl 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, non-conjugated group linked carbazoles, aza-carbazole / dibenzofuran / dibenzothiophene compounds, and high triplet state metal organometallic complexes (e.g., metal-carbene complexes).

[0454] e) Emitter materials in the EML:

[0455] One or more emitter materials can be used in conjunction with the compounds or devices of the present disclosure. The emitter materials can be emissive or non-emissive in the present devices as described herein. Examples of emitter materials are not particularly limited, and any compound can be used so long as the compound is capable of producing emission in a conventional OLED device. Examples of suitable emitter materials include, but are not limited to, compounds capable of producing emission via phosphorescence, non-delayed fluorescence, delayed fluorescence (especially thermally activated delayed fluorescence, i.e., TADF (also known as E-type delayed fluorescence)), triplet-triplet annihilation, or a combination of these methods.

[0456] In some embodiments, the emitter material has the formula M(L 1 ) x (L 2 ) y (L 3 ) z ;

[0457] wherein L 1 , L 2 , and L 3 may be the same or different;

[0458] wherein x is 1, 2, or 3;

[0459] wherein y is 0, 1, or 2;

[0460] wherein z is 0, 1, or 2;

[0461] wherein x + y + z is the oxidation state of the metal M;

[0462] wherein L 1 is selected from the group consisting of the structures in the following list of ligands:

[0463]

[0464]

[0465] wherein each L 2 and L 3 is independently selected from the group consisting of and the list of ligands; wherein:

[0466] M is selected from the group consisting of Ir, Rh, Re, Ru, Os, Pt, Pd, Zn, Au, Ag, and Cu;

[0467] T is selected from the group consisting of B, Al, Ga, and In;

[0468] K 1' is a direct bond or selected from the group consisting of NR e , PR e , O, S, and Se;

[0469] each Y 1 to Y 15 is independently selected from the group consisting of carbon and nitrogen;

[0470] Y' is selected from the group consisting of BR e , NR e , PR e , O, S, Se, C=0, S=0, S02, CR e R f , SiR e R f , and GeR e R f ;

[0471] each R a , R b , R c , and R d may independently represent mono-substitution to the maximum possible number of substitutions or no substitution;

[0472] 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 as defined herein; and

[0473] wherein any two substituents can be fused or joined to form a ring or form a polydentate ligand.

[0474] In some embodiments, the emitter material is selected from the group consisting of the following dopant Group 1 :

[0475]

[0476]

[0477]

[0478]

[0479] wherein

[0480] X 96 each of X 99 is independently C or N;

[0481] each Y 100 is independently selected from the group consisting of NR", O, S, and Se;

[0482] each of R 10a , R 20a , R 30a , R 40a , and R 50a independently represents mono-substitution, up to maximum substitution, or no substitution;

[0483] each of 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 is independently hydrogen or a substituent selected from the group consisting of the generic substituents defined herein; any two substituents can be joined or fused to form a ring.

[0484] In some embodiments, the emitter material is selected from the group consisting of the following dopant Group 2:

[0485]

[0486]

[0487]

[0488]

[0489]

[0490] wherein:

[0491] each Y 100 is independently selected from the group consisting of NR", O, S, and Se;

[0492] L is independently selected from the group consisting of a direct bond, BR", BR"R"', NR", PR", O, S, Se, C=0, C=S, C=Se, C=NR", C=CR"R"', S=0, S02, CR", CR"R"', SiR"R"', GeR"R"', alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof;

[0493] X 100 and X 200 is selected from the group consisting of O, S, Se, NR", and CR"R"' at each occurrence;

[0494] each R A” , R B” , R C” , R D” , R E” , and R F” independently represents mono-substitution, up to maximum substitution, or no substitution;

[0495] each of 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” is independently hydrogen or a substituent selected from the group consisting of the generic substituents as defined herein; any two substituents can be joined or fused to form a ring.

[0496] In some embodiments of the above dopant groups 1 and 2, each unsubstituted aromatic carbon atom can be replaced with N to form a nitrogen heterocycle. In some embodiments, the maximum number of N atoms in one ring is 1 or 2. In some embodiments of the above dopant group 2, the Pt atom in each formula can be replaced with a Pd atom.

[0497] In some embodiments of the OLED, the delayed fluorescence material comprises at least one donor group and at least one acceptor group. In some embodiments, the delayed fluorescence material is a metal complex. In some embodiments, the delayed fluorescence material is a non-metal complex. In some embodiments, the delayed fluorescence material is a Zn, Cu, Ag, or Au complex.

[0498] In some embodiments of the OLED, the delayed fluorescence material has the formula M(L 5 )(L 6 ), wherein M is Cu, Ag, or Au, L 5 and L 6 are different, and L 5 and L 6 are independently selected from the group consisting of:

[0499]

[0500]

[0501] wherein each A 1 -A 9 is independently selected from C or N;

[0502] each R P , R Q , and R U independently represents mono-substitution, up to maximum substitution, or no substitution;

[0503] wherein each R P , R P , R U , R SA , R SB , R RA , R RB , R RC , R RD , R RE , and R RF is independently hydrogen or a substituent selected from the group consisting of general substituents as defined herein; any two substituents can be joined or fused to form a ring.

[0504] In some embodiments of the OLED, the delayed fluorescence material comprises at least one of the donor moieties selected from the group consisting of:

[0505]

[0506]

[0507] wherein Y T , Y U , Y V , and Y Weach independently selected from the group consisting of B, C, Si, Ge, N, P, O, S, Se, C=0, S=0, and S02.

[0508] In some of the above embodiments, any carbon ring atom in each phenyl ring of any of the above structures up to a total of at most three carbon ring atoms together with its substituents can be replaced with N.

[0509] In some embodiments, the delayed fluorescence material comprises at least one of the acceptor moieties selected from the group consisting of nitrile, isonitrile, borane, fluoride, pyridine, pyrimidine, pyrazine, triazine, aza-carbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, aza-triphenylene, imidazole, pyrazole, oxazole, thiazole, isoxazole, isothiazole, triazole, thiadiazole, and oxadiazole. In some embodiments, the acceptor moieties and donor moieties as described herein can be connected directly, via a conjugated linker or a non-conjugated linker (e.g., sp 3 carbon or silicon atom).

[0510] In some embodiments, the fluorescent material comprises at least one of the chemical moieties selected from the group consisting of:

[0511]

[0512]

[0513] wherein Y F , Y G , Y H and Y I each independently selected from the group consisting of B, C, Si, Ge, N, P, O, S, Se, C=0, S=0, and S02;

[0514] wherein X F and X G each independently selected from the group consisting of C and N.

[0515] In some of the above embodiments, any carbon ring atom in each phenyl ring of any of the above structures up to a total of at most three carbon ring atoms together with its substituents can be replaced with N.

[0516] f) HBL:

[0517] A hole blocking layer (HBL) can be used to reduce the number of holes and / or excitons that escape from the emission layer. The presence of such a blocking layer in a device can result in substantially higher efficiency and / or longer lifetime compared to a similar device lacking a blocking layer. Furthermore, a blocking layer can be used to confine emission to a desired region of an OLED. In some embodiments, the HBL material has a lower HOMO (further from the vacuum level) and / or a higher triplet energy than one or more of the emitters nearest the HBL interface.

[0518] In some embodiments, the compounds used in the HBL contain the same molecule or the same functional group as used in the host described above.

[0519] In some embodiments, the compounds used in the HBL comprise at least one of the following moieties selected from the group consisting of:

[0520]

[0521] where k is an integer from 1 to 20; L 101 is another ligand, and k' is an integer from 1 to 3.

[0522] g) ETL:

[0523] An electron transport layer (ETL) can include a material capable of transporting electrons. The electron transport layer can be intrinsic (undoped) or doped. Doping can be used to enhance the conductivity. Examples of ETL materials are not particularly limited and can use any metal complex or organic compound as long as it is typically used to transport electrons.

[0524] In some embodiments, the compounds used in the ETL comprise at least one of the following moieties in the molecule: and fullerene; where k is an integer from 1 to 20, X 101 to X 108 selected from C or N; Z 101 selected from the group consisting of C, N, O, and S.

[0525] In some embodiments, the metal complex used in the ETL contains, but is not limited to, the following general formula:

[0526]

[0527] where (O-N) or (N-N) is a bidentate ligand with a metal coordinated to atoms O, N, or N,N; L 101 is another ligand; k' is an integer value from 1 to the maximum number of ligands that can be attached to the metal.

[0528] In some embodiments, the ETL material is selected from the group consisting of anthracene-benzimidazole compounds, aza-triphenylene derivatives, anthracene-benzothiazole compounds, metal 8-hydroxyquinolinate compounds, metal hydroxybenzoquinolinate compounds, bathocuprine compounds, 5-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(N^N) complexes.

[0529] h) Charge Generation Layer (CGL)

[0530] In tandem or stacked OLEDs, the CGL plays an essential role in performance, which consists of an n-doped layer and a p-doped layer for injecting electrons and holes, respectively. The electrons and holes are supplied by the CGL and electrodes. The electrons and holes consumed in the CGL are refilled by the electrons and holes injected from the cathode and anode, respectively; subsequently, the ambipolar current gradually reaches a steady state. Typical CGL materials include n- and p-conductivity dopants used in transport layers.

[0531] In any of the compounds described herein, the hydrogen atoms can be partially or fully deuterated. The minimum amount of hydrogen in the compound that is deuterated is selected from the group consisting of 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 99%, and 100%. As used herein, the percentage deuterated has its ordinary meaning and includes the percentage of all possible hydrogen and deuterium atoms replaced by deuterium atoms. In some embodiments, the deuterium atoms are attached to aromatic rings. In some embodiments, the deuterium atoms are attached to saturated carbon atoms, such as alkyl or cycloalkyl carbon atoms. In some other embodiments, the deuterium atoms are attached to heteroatoms, such as Si or Ge atoms.

[0532] It should be understood that the various embodiments described herein are by way of example only, and are not intended to limit the scope of the invention. For example, many of the materials and structures described herein can be substituted with other materials and structures without deviating from the spirit of the invention. The invention as claimed is thus intended to include, among other things, the embodiments described herein, as well as equivalents thereto. It is also to be understood that the various theories as to why the invention works are not intended to be limiting.

[0533] E. Experimental Data

[0534] Synthesis of Representative Compounds 1-5

[0535] Synthesis of Compound 1:

[0536]

[0537]

[0538] Synthesis of 6-dibromo-3,5-dimethylphenol (1-A)

[0539] A mixture of bromine (4.2 mL, 81.85 mmol, 2 eq) and tert-butylamine (17.3 mL, 163.7 mmol, 4 eq) in toluene (165 mL) was stirred at -30 °C for 30 min (solution A). Solution A was added slowly to a solution of 3,5-dimethylphenol in toluene (204 mL) at -30 °C. The mixture was then stirred at -30 °C for 30 min and at room temperature for 15 h. The reaction was quenched by saturated sodium bicarbonate (50 mL). The mixture was transferred to a separatory funnel and extracted with ethyl acetate (100 mL x 3). The combined organic layers were washed with brine (200 mL), dried over sodium sulfate, and concentrated under reduced pressure. The crude material was adsorbed onto celite (60 g) (celite) and purified by chromatography to give 1-A as a colorless oil (9.55 g, 67% yield).

[0540] Synthesis of 2,4-dibromo-3-methoxy-1,5-dimethylbenzene (1-B)

[0541] A mixture of 1-A (9.55 g, 34.11 mmol, 1 eq), potassium carbonate (14.14 g, 102.3 mmol, 3 eq), and iodomethane (6.37 mL, 102.3 mmol, 3 eq) in methanol (148 mL) was heated at reflux for 15 h. The reaction mixture was cooled to room temperature and quenched with saturated ammonium chloride solution (50 mL). The mixture was extracted with dichloromethane (150 mL x 3). The combined organic layers were washed with brine (200 mL), dried over sodium sulfate, and concentrated under reduced pressure. The crude material was adsorbed onto celite (50 g) and purified by chromatography to give 1-B as a white solid (8.08 g, 73% yield).

[0542] Synthesis of 2,4-dibromo-3-methoxy-1,5-bis(methyl-d3)benzene (1-C)

[0543] A mixture of 1-B (8.08 g, 27.48 mmol, 1 eq) and sodium tert-butoxide (0.78 g, 8.25 mmol, 0.3 eq) in deuterated DMSO (58 mL) was bubbled with nitrogen for 10 min and heated to 70 °C. After 7 h, the reaction mixture was cooled to room temperature and quenched with D2O (10 mL). The reaction mixture was extracted with dichloromethane (30 mL x 3). The combined organic layers were washed with brine (40 mL), dried over sodium sulfate, and concentrated under reduced pressure to give 1-C as a white solid (7.1 g, 78% yield).

[0544] Synthesis of 2,6-dibromo-3,5-bis(methyl-d3)phenol (1-D)

[0545] A solution of 1-C (7.1 g, 23.67 mmol, 1 eq) in anhydrous dichloromethane (95 mL) was cooled to -78 °C. 1M boron tribromide (24.85 mL, 24.85 mmol, 1.05 eq) was added dropwise to the solution at -78 °C. The reaction mixture was stirred at -78 °C for 2 h and then warmed to room temperature and stirred for 15 h. The reaction was quenched by the addition of water (50 mL). The mixture was transferred to a separatory funnel containing saturated sodium bicarbonate (100 mL). The aqueous phase was extracted with dichloromethane (3 x 50 mL). The combined organic phase was washed with brine (100 mL), dried over sodium sulfate, and concentrated under reduced pressure. The crude material was adsorbed onto celite (40 g) and purified on a chromatography system to give 1-D (6.0 g, 85% yield).

[0546] Synthesis of 4',6'-bis(methyl-d3)-[1,1':3',1"-terphenyl]-2,2",3,3",4,4",5,5",6,6"-d10-2'-ol (1-E)

[0547] A mixture of 1-D (6 g, 20.98 mmol, 1 eq), tetrakis(triphenylphosphine)palladium(0) (2.42 g, 2.1 mmol, 0.1 eq), (phenyl-d5)boronic acid (10.65 g, 83.92 mmol, 4 eq), and potassium phosphate tribasic (19.32 g, 83.92 mmol, 4 eq) in a 10:1 mixture of dioxane and water (210 mL) was bubbled with nitrogen for 15 min. The reaction mixture was stirred at 100 °C for 16 h. The mixture was transferred to a separatory funnel and extracted with diethyl ether (100 mL x 3). The combined organic layers were washed with brine (200 mL), dried over sodium sulfate, and concentrated under reduced pressure. The crude material was adsorbed onto celite (40 g) and purified to give 1-E (3.9 g, 64% yield) as a white solid.

[0548] Synthesis of 4',6'-bis(methyl-d3)-[1,1':3',1"-terphenyl]-2'-yl-2,2",3,3",4,4",5,5",6,6"-d10 trifluoromethanesulfonate (1-F)

[0549] To a solution of 1-E (3.9 g, 13.43 mmol, 1 equiv) and pyridine (2.3 mL, 28.2 mmol, 2.1 equiv) in anhydrous dichloromethane (67 mL) was added triflic anhydride (3.39 mL, 20.14 mmol, 1.5 equiv) at 0 °C. The reaction mixture was stirred at room temperature. After 15 h, the mixture was diluted with dichloromethane (150 mL) and water (150 mL). The layers were separated and the aqueous layer was extracted with dichloromethane (2 x 200 mL). The combined organic layers were dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was adsorbed onto diatomite (30 g) and purified on a chromatography system to give 1-F as a white solid (5.28 g, 93% yield).

[0550] Synthesis of N1-(4',6'-bis(methyl-d3)-[1,1':3',1"-terphenyl]-2'-yl-2,2",3,3",4,4",5,5",6,6"-d10)benzene-1,2-diamine (1-G)

[0551] A mixture of 1-F (4 g, 9.47 mmol, 1 equiv), benzene-1,2-diamine (2.05 g, 18.93 mmol, 2 equiv), and BINAP Pd G3 (0.94 g, 0.95 mmol, 0.1 equiv), cesium carbonate (9.25 g, 28.4 mmol, 3 equiv) in anhydrous toluene (97 mL) was bubbled with nitrogen for 20 min. After heating at 110 °C for 2 days, LC / MS analysis indicated 80% conversion. Additional BINAP Pd G3 (0.94 g, 0.95 mmol, 0.1 equiv), cesium carbonate (4.63 g, 14.2 mmol, 1.5 equiv), and benzene-1,2-diamine (1.02 g, 9.47 mmol, 1 equiv) were added. The mixture was bubbled with nitrogen for 15 min and stirred at 110 °C. After 18 h, the reaction was cooled to room temperature. It was diluted with water (100 mL). The aqueous phase was extracted with ethyl acetate (2 x 200 mL). The combined organic layers were dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was adsorbed onto diatomite (30 g) and purified on a chromatography system to give 1-G as an off-white solid (2.44 g, 68% yield).

[0552] Synthesis of N1-(4',6'-bis(methyl-d3)-[1,1':3',1"-terphenyl]-2'-yl-2,2",3,3",4,4",5,5",6,6"-d10)-N2-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)benzene-1,2-diamine (1-I)

[0553] A mixture of 1-G (2.22 g, 5.83 mmol, 1 equiv), H (3.03 g, 6.42 mmol, 1.1 equiv), and BINAP Pd Gen3 (0.58 g, 0.58 mmol, 0.1 equiv) in anhydrous toluene (29 mL) was bubbled with nitrogen for 20 minutes. Sodium tert-butoxide (1.12 g, 11.67 mmol, 2 equiv) was added and the mixture was bubbled with nitrogen for another 5 minutes. After heating at 110 °C for 16 hours, the reaction mixture was cooled to room temperature and concentrated under reduced pressure. The crude material was adsorbed onto celite (20 g) and purified by chromatography to give 1-I as a brown solid (4.2 g, 91% yield).

[0554] 3-(4',6'-Bis(methyl-d3)-[1,1':3',1"-terphenyl]-2'-yl-2,2",3,3",4,4",5,5",6,6"-d10)-1-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-1H-benzo[d]imidazolium chloride (1-J) Synthesis

[0555] A solution of 1-I (2.02 g, 2.62 mmol, 1 equiv) in triethyl orthoformate (22 mL) was bubbled with nitrogen for 15 minutes and then charged with concentrated deuterium chloride (0.65 mL, 7.86 mmol, 3 equiv). The reaction was heated at 100 °C in a pressure tube for 3 hours, cooled to room temperature and concentrated under reduced pressure to remove most of the triethyl orthoformate. The resulting residue was triturated with diethyl ether (40 mL) and filtered to give 1-J as an off-white solid (2.24 g, 96% yield).

[0556] 3-(4',6'-Bis(methyl-d3)-[1,1':3',1"-terphenyl]-2'-yl-2,2",3,3",4,4",5,5",6,6"-d10)-1-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-1H-benzo[d]imidazolium chloride (1-J) Synthesis

[0557] A mixture of 1-J (2.14 g, 2.61 mmol, 1 eq) and potassium tetrachloroplatinate (1.19 g, 2.87 mmol, 1.1 eq) in acetic acid (52 mL) was bubbled with nitrogen for 15 minutes and 2,6-dimethylpyridine (1 mL, 8.62 mmol, 3.3 eq) was added. The reaction was heated at 120 °C in a pressure tube. After 15 hours, the reaction mixture was cooled to room temperature, poured into water (100 mL) and stirred for 10 minutes. The resulting precipitate was filtered and washed with water (3 x 150 mL) followed by methanol (3 x 150 mL). The solid was dissolved in dichloromethane, dried over sodium sulfate, filtered and concentrated under reduced pressure. The crude material was adsorbed onto celite (30 g) and purified on a chromatography system to give compound 1 (2 g, 98% UHPLC purity). The product was further purified by preparative HPLC to give a yellow solid.

[0558]

[0559] Synthesis of 4-bromo-2,6-dichloro-3,5-dimethylaniline (SM-B)

[0560] N-chlorosuccinimide (22.42 g, 2.1 eq, 167.9 mmol) was added to a solution of compound SM-A (16.00 g, 1 eq, 79.97 mmol) in anhydrous DMF (301.8 mL) under nitrogen. The mixture was stirred at room temperature for 16 hours. The reaction mixture was transferred to a separatory funnel containing sodium thiosulfate (200 mL) and ethyl acetate (200 mL). The aqueous layer was extracted with ethyl acetate (100 mL x 2). The combined organic layers were washed with brine (200 mL), dried over sodium sulfate, filtered and concentrated. It was purified on a chromatography system to give compound SM-B (17.6 g, 80% yield) as a white solid.

[0561] Synthesis of 2,6-dichloro-3,5-dimethylbenzene-4-d-amine (SM-C)

[0562] To a solution of compound SM-B (12.00 g, 1 eq, 41.05 mmol) in anhydrous tetrahydrofuran (410 mL) at -78 °C was added n-butyllithium (49.26 mL, 2.5 M, 3 eq, 123.1 mmol). The mixture was stirred at -78 °C for 1 hour. Deuterium oxide (7.43 mL, 10 eq, 410.5 mmol) was then added. The mixture was allowed to warm to room temperature and stirred for 15 hours. The reaction mixture was concentrated under reduced pressure and purified by chromatography to give compound SM-C (7.88 g, 78% yield) as a white solid.

[0563] Synthesis of 2,6-dichloro-3,5-bis(methyl-d3)aniline (SM-D)

[0564] A solution of compound SM-C (7.82 g, 40.93 mmol, 1 eq) in DMSO (227 mL) was bubbled with nitrogen for 15 minutes. Sodium tert-butoxide (2.36 g, 24.56 mmol, 0.6 eq) was added to the reaction mixture. It was stirred at 60 °C for 16 hours. It was cooled to 0 °C and quenched with deuterium oxide (10 mL). This mixture was transferred to a separatory funnel containing water (100 mL). It was extracted with diethyl ether (3 x 200 mL), washed with water (300 mL x 2) and brine (300 mL x 2), dried over sodium sulfate to get the crude material. The material was subjected to H / D exchange conditions again. After stirring at 60 °C for 18 hours, the reaction mixture was cooled to 0 °C and quenched with deuterium oxide (10 mL). This mixture was transferred to a separatory funnel containing water (100 mL). It was extracted with diethyl ether (3 x 200 mL), washed with water (300 mL x 2) and brine (300 mL x 2), dried over sodium sulfate. The crude material was purified by chromatography to get compound SM-D (5.68 g, 70% yield) as a white solid.

[0565] Synthesis of 2,6-dichloro-3,5-bis(methyl-d3)-N-(2-nitrophenyl)aniline (SM-E)

[0566] To a solution of SM-D (5.54 g, 28.11 mmol, 1 eq) in anhydrous NMP (56 mL) at 0 °C under nitrogen was added sodium hydride (2.81 g, 70.27 mmol, 2.5 eq). It was stirred for 15 minutes. Then 1-fluoro-2-nitrobenzene (4.16 g, 29.51 mmol, 1.05 eq) was added dropwise at 0 °C. The mixture was warmed to room temperature and stirred overnight. Deuterium oxide (10 mL) was added to the reaction mixture followed by water (100 mL). The mixture was stirred for 30 minutes. Then the resulting mixture was filtered, washed with water (20 mL x 3) and hexane (40 mL x 2). Then the yellow filter cake was collected and dried under reduced pressure for 3 hours to get compound SM-E (6.7 g, 75% yield) as a yellow solid.

[0567] Synthesis of N1-(2,6-dichloro-3,5-bis(methyl-d3)phenyl)benzene-1,2-diamine (SM-F)

[0568] A mixture of compound SM-E (6.98 g, 21.93 mmol, 1 eq), iron (6.13 g, 109.7 mmol, 5 eq) and concentrated hydrogen chloride (8.3 mL, 99.57 mmol, 12.00 molar, 4.54 eq) in ethanol (110 mL) was heated to reflux for 2.5 hours. The mixture was filtered through celite. The filtrate was concentrated under reduced pressure. It was diluted with ethyl acetate (100 mL). It was washed with water (100 mL x 2) and saturated sodium bicarbonate solution (100 mL x 2), dried over sodium sulfate. The crude material was purified by column chromatography to afford compound SM-F (4 g, 63% yield) as a brown solid.

[0569] Synthesis of N1-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-N2-(2,6-dichloro-3,5-bis(methyl-d3)phenyl)benzene-1,2-diamine (SM-G)

[0570] A mixture of SM-F (3.93 g, 13.64 mmol, 1 eq), compound H (6.75 g, 14.32 mmol, 1.05 eq) and BINAP Pd Gen3 (0.677 g, 0.68 mmol, 0.05 eq) in anhydrous toluene (68 mL) was bubbled with nitrogen for 20 minutes. Sodium tert-butoxide (2.62 g, 27.3 mmol, 2 eq) was added. The mixture was bubbled with nitrogen for another 5 minutes and heated at 110 °C for 20 hours. The reaction mixture was cooled to room temperature and concentrated under reduced pressure. The crude material was purified by chromatography to afford SM-G (5 g, 54% yield) as a brown solid.

[0571] Synthesis of 1-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-3-(2,6-dichloro-3,5-bis(methyl-d3)phenyl)-1H-benzo[d]imidazol-3-ium chloride (SM-H)

[0572] A solution of compound SM-G (5.3 g, 7.8 mmol, 1 eq) in triethyl orthoformate (65 mL) was bubbled with nitrogen for 15 minutes. Concentrated deuterium chloride (1.95 mL, 23.4 mmol, 3 eq) was added and the reaction was heated to 100 °C in a pressure tube for 3 hours. The reaction mixture was cooled to room temperature and concentrated under reduced pressure to remove most of the triethyl orthoformate. The resulting residue was triturated with diethyl ether (200 mL) and filtered to afford SM-H (5.36 g, 94% yield) as a beige solid.

[0573] Synthesis of platinum (II) complex of 1 -(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-3-(2,6-dichloro-3,5-bis(methyl-d3)phenyl)-1 H-benzo[d]imidazole (SM)

[0574] A mixture of SM-H (5.3 g, 7.3 mmol, 1 equiv) and potassium tetrachloroplatinate (3.34 g, 8.04 mmol, 1.1 equiv) in acetic acid (146 mL) was bubbled with nitrogen for 15 min and 2,6-dimethylpyridine (2.81 mL, 24.1 mmol, 3.3 equiv) was added. The reaction was stirred at 120 °C for 15 h. It was diluted with water (100 mL) and extracted with dichloromethane (100 mL x 3). The combined organic layers were washed with water (150 mL) and brine (150 mL), dried over sodium sulfate and concentrated. The crude material was adsorbed onto celite (80 g) and purified on a chromatography system to give SM as a yellow solid (5 g, 77% yield).

[0575]

[0576] Synthesis of platinum (II) complex of 1 -(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-3-(3,3”,5,5”-tetra-tert-butyl-4’,6’-bis(methyl-d3)-[1,1’:3’,1 ”-terphenyl]-2’-yl)-1 H-benzo[D]imidazole (Compound 2)

[0577] A mixture of SM (500 mg, 1 equiv, 483 pmol), SPhos Pd G2 (210 mg, 0.6 equiv, 0.29 mmol), (3,5-di-tert-butylphenyl)boronic acid (2.03 g, 18 equiv, 8.7 mmol) and potassium phosphate tribasic monohydrate (2 g, 18 equiv, 8.7 mmol) in a 10:1 mixture of dioxane and water (7 mL) was bubbled with nitrogen for 15 min. It was stirred at 100 °C for 3 days. The mixture was filtered through a plug of celite and washed with dichloromethane (200 mL). The filtrate was concentrated under reduced pressure. The crude material was purified by chromatography to give Compound 2 (570 mg, 97.7% purity).

[0578]

[0579] Synthesis of platinum (II) complex of 3-(3,5-bis(methyl-d3)-2,6-bis(5,5,8,8-tetra(methyl-d3)-5,6,7,8-tetrahydronaphthalen-2-yl-1,3,4,6,6,7,7-d7)phenyl)-1-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-1H-benzo[d]imidazole (Compound 3)

[0580] A mixture of SM (920 mg, 1 eq, 1.05 mmol), SPhos Pd G2 (151 mg, 0.2 eq, 0.21 mmol), (5,5,8,8-tetra(methyl-d3)-5,6,7,8-tetrahydronaphthalen-2-yl-1,3,4,6,6,7,7-d7)boronic acid (2.100 g, 8 eq, 8.36 mmol), and potassium phosphate tribasic monohydrate (1.92 g, 8 eq, 8.36 mmol) in a 10:1 mixture of dioxane and water (12 mL) was bubbled with nitrogen for 15 minutes. It was heated to 100 °C for 18 hours. The mixture was filtered through a plug of celite and washed with dichloromethane (200 mL). The filtrate was concentrated under reduced pressure. The crude material was purified by chromatography to give the mono-coupled product (796 mg, 88% HPLC purity) and Compound 3 (118 mg, 91% purity). The mono-coupled product (1.10 g, 1 eq, 1.05 mmol) was treated with SPhos Pd G2 (151 mg, 0.2 eq, 0.21 mmol), (5,5,8,8-tetra(methyl-d3)-5,6,7,8-tetrahydronaphthalen-2-yl-1,3,4,6,6,7,7-d7)boronic acid (2.10 g, 8 eq, 8.37 mmol), and potassium phosphate tribasic monohydrate (1.92 g, 8 eq, 8.36 mmol) in a mixture of dioxane and water (12 mL) at 100 °C for 20 hours. LC / MS analysis indicated 35% conversion. Additional SPhos Pd G2 (151 mg, 0.2 eq, 0.21 mmol), (5,5,8,8-tetra(methyl-d3)-5,6,7,8-tetrahydronaphthalen-2-yl-1,3,4,6,6,7,7-d7)boronic acid (2.10 g, 8 eq, 8.37 mmol), and potassium phosphate tribasic monohydrate (1.92 g, 8 eq, 8.36 mmol) were added. The solution was bubbled with nitrogen for 10 minutes and stirred at 100 °C for 1 day. The mixture was filtered through a plug of celite and washed with dichloromethane (200 mL). The filtrate was concentrated under reduced pressure.

[0581] The crude material was purified by chromatography to give Compound 3 (670 mg, 52% yield).

[0582]

[0583] 3-(4',6'-bis(methyl-d3)-3,3"-bis(tris(phenyl-d5)silyl)-[1,1':3',1"-terphenyl]-2'-yl- 2,2",4,4",5,5",6,6"-d8)-1-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)- 1H-benzo[d]imidazole (Compound 4)

[0584] A mixture of SM (800 mg, 1 equiv, 907 pmol) and SPhos Pd G2 (131 mg, 0.2 equiv, 182 pmol), (3-(tris(phenyl-d5)silyl)phenyl-2,4,5,6-d4)boronic acid (2.9 g, 8 equiv, 7.26 mmol), and potassium phosphate tribasic monohydrate (1.67 g, 8 equiv, 7.26 mmol) in a 10:1 mixture of dioxane and water (10 mL) was bubbled with nitrogen for 15 minutes. It was heated to 100 °C for 19 hours. The mixture was filtered through a plug of celite and washed with dichloromethane (200 mL). The filtrate was concentrated under reduced pressure. The crude material was purified by automated chromatography to give the mono-coupled product (672 mg, 85% purity) and Compound 4 (400 mg, 96% HPLC purity). The mono-coupled product (0.46 g, 1 equiv, 0.39 mmol) was treated with SPhos Pd G2 (0.168 g, 0.6 equiv, 0.231 mmol), (3-(tris(phenyl-d5)silyl)phenyl-2,4,5,6-d4)boronic acid (2.32 g, 15 equiv, 5.79 mmol), and potassium phosphate tribasic monohydrate (1.48 g, 15 equiv, 5.79 mmol) in a 10:1 mixture of dioxane and water (6 mL) at 100 °C for 3 days. The mixture was filtered through a plug of celite and washed with dichloromethane (150 mL). The filtrate was concentrated under reduced pressure. The crude material was purified by chromatography to give Compound 4 (720 mg, 96% purity).

[0585]

[0586] Synthesis of platinum(II) complex of 1-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2- yl)oxy)phenyl)-3-(2-chloro-3,5-bis(methyl-d3)-6-(5,5,8,8-tetra(methyl-d3)-5,6,7,8- tetrahydronaphthalen-2-yl-1,3,4,6,6,7,7-d7)phenyl)-1H-benzo[d]imidazole (5-A):

[0587] A mixture of SM (1.0 g, 1 equiv, 1.13 mmol), SPhos Pd G2 (163.5 mg, 0.2 equiv, 0.23 mmol), (5,5,8,8-tetra(methyl-d3)-5,6,7,8-tetrahydronaphthalen-2-yl-1,3,4,6,6,7,7-d7)boronic acid (2.28 g, 8 equiv, 9.07 mmol), and potassium phosphate tribasic monohydrate (2.09 g, 8 equiv, 9.07 mmol) in a 10:1 mixture of dioxane and water (13 mL) was bubbled with nitrogen for 15 minutes. It was heated to 100 °C for 18 hours. The mixture was cooled to room temperature and filtered through a plug of celite. The filtrate was concentrated under reduced pressure and purified by chromatography to give 5-A as a yellow solid (828 mg, 69% yield).

[0588] 3-(4,6-bis(methyl-d3)-3-(5,5,8,8-tetra(methyl-d3)-5,6,7,8-tetrahydronaphthalen-2-yl-1,3,4,6,6,7,7-d7)-3'-(tris(phenyl-d5)silyl)-[1,1'-biphenyl]-2-yl-2',4',5',6'-d4)-1-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-1H-benzo[d]imidazole platinum(II) complex (Compound 5) Synthesis

[0589] A mixture of 5-A (828.0 mg, 1 equiv, 0.79 mmol), SPhos Pd G2 (113 mg, 0.2 equiv, 0.16 mmol), (3-(tri(phenyl-d5)silyl)phenyl-2,5,6-d3)boronic acid (2.507 g, 8 equiv, 6.29 mmol), and potassium phosphate tribasic monohydrate (1.34 g, 8 equiv, 6.29 mmol) in a 10:1 mixture of dioxane and water (9 mL) was bubbled with nitrogen for 15 minutes. It was stirred at 100 °C for 18 hours. Additional SPhos Pd G2 (113 mg, 0.2 equiv, 0.16 mmol), (3-(tri(phenyl-d5)silyl)phenyl-2,5,6-d3)boronic acid (2.507 g, 8 equiv, 6.29 mmol), and potassium phosphate tribasic monohydrate (1.34 g, 8 equiv, 6.29 mmol) were added. It was bubbled with nitrogen for 10 minutes followed by stirring at 100 °C for 1 day. Additional SPhos Pd G2 (113 mg, 0.2 equiv, 0.16 mmol), (3-(tri(phenyl-d5)silyl)phenyl-2,5,6-d3)boronic acid (2.507 g, 8 equiv, 6.29 mmol), and potassium phosphate tribasic monohydrate (1.34 g, 8 equiv, 6.29 mmol) were added. It was bubbled with nitrogen for 10 minutes followed by stirring at 100 °C for 1 day. The mixture was filtered through a plug of celite and washed with dichloromethane (200 mL). The filtrate was concentrated under reduced pressure. The crude material was purified by chromatography to afford compound 5 (590 mg, 55% yield).

[0590] Photophysical characterization

[0591]

[0592]

[0593]

[0594]

[0595] The above compounds 1-5 of the present invention show a significant blue shift relative to their comparative compounds. The addition of the 3,5-dimethyl group successfully modulates the spatial rigidity required for the blue shift, ranging between 2-4 nm in thin films of the phosphor doped into a PMMA matrix. These numbers are well beyond any value attributable to experimental error, and the observed improvement is significant and unexpected. The blue shift achieved makes the phosphor employing the structural motif of the present invention more suitable for application as a deep blue phosphor required for display technology. The magnitude of the blue shift obtained indicates that the structural motif of the present invention can be used to tune the color of a variety of Pt complexes based on the scaffold outlined in Formula I.

[0596] Emission spectra and resulting λmax values were collected using a Hamamatsu Quantaurus-QY Plus UV-NIR absolute PL quantum yield spectrometer with an excitation wavelength of 340 nm. A 1% emitter solution in PMMA in toluene was prepared, filtered, and cast dropwise onto a quartz substrate.

Claims

1. A compound comprising Formula I: Formula I wherein: M is Pt, Pd, or Au; moiety A is a 5- or 6-membered ring; each of moiety B, moiety C, and moiety D is independently a monocyclic or polycyclic fused ring system, wherein each ring of the monocyclic or the polycyclic fused ring system is independently a 5- to 10-membered carbocyclic or heterocyclic ring; any two substituents can be joined or fused to form a ring. or the structure of Formula I' wherein:

2. The compound of claim 1, wherein each of moiety B and moiety C and moiety D is independently selected from the group consisting of cyclic moieties defined herein. each is independently a single or double bond; 3. The compound of claim 1, wherein moiety B is selected from the group consisting of benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, imidazole- derived carbene, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole, and triazole; and / or wherein moiety C is selected from the group consisting of naphthalene, quinoline, isoquinoline, quinazoline, benzofuran, azabenzofuran, phenanthro[3,2-b]benzofuran, benzoxazole, azabenzoxazole, benzothiophene, azabenzothiophene, benzothiazole, azabenzothiazole, benzaselenophene, azabenzaselenophene, indene, azaindene, indole, azaindole, benzoimidazole, benzoimidazole-derived carbene, azabenzimidazole, benzo-benzoimidazole, azabenzobenzoimidazole, carbazole, azacarbazole, diphenylene, azadiphenylene, thianthrene, phenoxazine, phenanthrene, azaphenanthrene, anthracene, azanthracene, phenanthridine, fluorene, and azaf luorene; and / or wherein moiety D is selected from the group consisting of pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, pyrazole, pyrrole, oxazole, thiazole, and triazole.

4. The compound of claim 1, wherein: moiety B is selected from the group consisting of benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, pyrazole, pyrrole, oxazole, thiazole, and triazole; and / or wherein moiety C is selected from the group consisting of naphthalene, quinoline, isoquinoline, quinazoline, benzofuran, azabenzofuran, phenanthro[3,2-b]benzofuran, benzoxazole, azabenzoxazole, benzothiophene, azabenzothiophene, benzothiazole, azabenzothiazole, benzaselenophene, azabenzaselenophene, indene, azaindene, indole, azaindole, benzoimidazole, benzoimidazole-derived carbene, azabenzimidazole, benzo-benzoimidazole, azabenzobenzoimidazole, carbazole, azacarbazole, diphenylene, thianthrene, phenoxazine, phenanthrene, azaphenanthrene, anthracene, azanthracene, phenanthridine, fluorene, and azaf luorene; and / or wherein moiety D is selected from the group consisting of pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, pyrazole, pyrrole, oxazole, thiazole, and triazole. X 1 to X 8 , Z 1 , Z 2 and Z 3 each independently is C or N; X 9 is CR E or N; K 1 and K 2 each independently is selected from the group consisting of a direct bond, O, S, N(R α ), P(R α ), B(R α ), C(R α )(R β ), and Si(R α )(R β ); L 1 to L 3 each of R, R', and R" is independently selected from the group consisting of a direct bond, BR, BRR', NR, PR, P(0)R, O, S, Se, C=0, C=S, C=Se, C=NR', C=CRR', S=0, S02, CR, CRR', SiRR', and GeRR'; R A , R B , R C , and R D each independently represents mono-substitution to the maximum allowable substitution, or no substitution; each R, R', R α , R β , R A , R B , R C , R D , R E , R F , R F' , R G' , and R G' are each independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, selenoalkyl, and combinations thereof, wherein at least one of R F and R F' is not hydrogen, and at least one of R G and R G is not hydrogen; and 5. The compound of claim 1, wherein: any two substituents can be joined or fused to form a ring.

11. The compound of claim 1, wherein the compound has a structure selected from the group consisting of: wherein R1through R437have the following structures:

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

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

4. The compound according to claim 1, wherein Z 1 and Z 2 Is it C or Z among them? 1 or Z 2 Any one of them is N and Z 1 or Z 2 The other one is C; and / or where X is... 1 To X 8 Each of them is C or where X is a C. 1 To X 8 At least one of them is N; and / or where K is K 1 It is a direct bond, O or S; and / or where L is a direct bond. 1 Choose from the group consisting of O, BR, NR, CRR', SiRR', S, and Se; and / or L among them. 2 Select the group consisting of direct bonds, O, BR, NR, CRR', SiRR', S, and Se; and / or L. 3 Select the group consisting of free direct bonds, O, BR, NR, CRR', SiRR', S, and Se; and / or X. 9 It is CR E .

5. The compound of claim 1, wherein the compound comprises the structure of Formula II .

6. The compound of claim 1, wherein R F and R G are fused to comprise a structure of Formula IA wherein Y 1 is O, S, or NR.

7. The compound of claim 1, wherein R F' and R G' are fused to comprise a structure of Formula IB wherein Y 2 is O, S, or NR.

8. The compound of claim 1, wherein at least one R A comprises a substituent selected from the group consisting of alkyl, cycloalkyl, silyl, germyl, aryl, heteroaryl, and combinations thereof; and / or wherein at least one R B comprises a substituent selected from the group consisting of alkyl, cycloalkyl, silyl, germyl, aryl, heteroaryl, and combinations thereof; and / or wherein at least one R C comprises a substituent selected from the group consisting of alkyl, cycloalkyl, silyl, germyl, aryl, heteroaryl, and combinations thereof; and / or wherein at least one R D comprises a substituent selected from the group consisting of alkyl, cycloalkyl, silyl, germyl, aryl, heteroaryl, and combinations thereof; and / or wherein R E is present and comprises a substituent selected from the group consisting of alkyl, cycloalkyl, silyl, germyl, aryl, heteroaryl, and combinations thereof; and / or wherein at least one R F or R F' comprises a substituent selected from the group consisting of alkyl, cycloalkyl, silyl, germyl, aryl, heteroaryl, and combinations thereof; and / or wherein at least one R G or R G' comprises a substituent selected from the group consisting of alkyl, cycloalkyl, silyl, germyl, aryl, heteroaryl, and combinations thereof; and / or wherein M is Pt or Pd.

9. The compound of claim 1, wherein two R A bonded or fused to form a moiety A1 fused to ring A, wherein moiety A1 is a monocyclic or polycyclic fused ring system, wherein each ring in the monocyclic or polycyclic fused ring system is independently a 5- to 10-membered carbocyclic or heterocyclic ring.

10. The compound of claim 1, wherein the compound is selected from the group consisting of compounds of formula Pt(L A' )(Ly). wherein L A' is selected from the group consisting of the structures in List 3 below: wherein L y is selected from the group consisting of the structures of List 4 below:

15. A consumer product comprising an organic light emitting device, the organic light emitting device comprising: an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises a compound of claim 1. R E' represents di-substitution to the maximum allowable substitution; R E" represents mono-substitution to the maximum allowable substitution; each R E' , R E" , R H , R H' , R X , and R Y are independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boryl, aralkyl, alkoxy, aryloxy, amino, silyl, germyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfido, sulfinyl, sulfonyl, phosphino, selenoalkyl, and combinations thereof; ​ ​ wherein each of R A1 , R A2 , R B1 , R B2 , R C1 , R C2 , R D1 , R D2 , R E1 , R FF1 , R FF2 , R FF3 , R GG1 , R GG2 , R H1 , and R H2 is independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, selenoalkyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

12. The compound of claim 1, wherein the compound is selected from the group consisting of compounds of formula Pt(L A' )(Ly). wherein L A' is selected from the group consisting of [L A' i-(Ri)(Rj)(Rk)(Rl), L A' i'-(Ri)(Rj)(Rk)(Rl), L A' i"(Ri)(Rj)(Rk)(Rl), and L A' i'"-(Ri)(Rj)(Rk)(Rl). wherein for L A' i-(Ri)(Rj)(Rk)(Rl), i is an integer from 1 to 16, and L A' i-(Ri)(Rj)(Rk)(Rl) is selected from the group consisting of L A' 1-(R2)(R2)(R1)(R1) to L A' 16-(R437)(R437(R437)(R437) of the compounds and L A' 1-(R2)(R1)(R2)(R1) to L A' 16-(R437)(R437(R437)(R437) of the compounds; wherein for L A' i'-(Ri)(Rj)(Rk)(Rl), i' is an integer from 17 to 23, and L A' i'-(Ri)(Rj)(Rk)(Rl) is selected from the group consisting of L A' 17-(R2)(R2)(R1)(R1) to L A' 23-(R437)(R437(R437)(R437) and L A' 17-(R2)(R1)(R1)(R2) to L A' 23-(R437)(R437(R437)(R437). wherein for L A' i"(Ri)(Rj)(Rk)(Rl), i" is an integer from 24 to 32, and L A' i"(Ri)(Rj)(Rk)(Rl) is selected from the group consisting of L A' 24-(R2)(R1)(R1)(R1) to L A' 32-(R437)(R437(R437)(R437) of the formula: wherein for L A' i'"-(Ri)(Rj)(Rk)(Rl), i'" is 33, and L A' i'"-(Ri)(Rj)(Rk)(Rl) is selected from the group consisting of L A' 33-(R2)(R1)(R1)(R1) to L A' 33-(R437)(R437(R437)(R437) of the compounds and L A' 33-(R1)(R1)(R1)(R2) to L A' 33-(R437)(R437(R437)(R437) of the compounds, and wherein L A'i - (Ri)(Rj)(Rk)(Rl), L A'i' - (Ri)(Rj)(Rk)(Rl), L A'I" - (Ri)(Rj)(Rk)(Rl), and L A'i"' - each of (Ri)(Rj)(Rk)(Rl) is defined in List 7 below: wherein L y selected from L y n-(Rs)(Rt)(Ru)(Rv), wherein n is an integer from 1 to 68, and each of Rs, Rt, Ru, and Rv is independently selected from R1 to R437, and L y 1-(R1)(R1)(R1)(R1) to L y 68-(R437)(R437)(R437)(R437), each of which is defined in List 8 below: ​ ​ ​ ​ ​ ​ ​ ​ ​ ​

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