Organic electroluminescent materials and devices

Abstract

The invention relates to organic electroluminescent materials and devices. Organometallic compounds comprising one central metal atom and at least one at least bidentate ligand comprising at least two moieties independently being a monocyclic or polycyclic fused ring system wherein each ring of the monocyclic or polycyclic fused ring system is independently a 5-to 10-membered carbocyclic or heterocyclic ring are provided. Formulations comprising these organometallic compounds are also provided. Organic light emitting devices (OLED) and related consumer products utilizing these organometallic compounds are also provided.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority under 35 USC §119(e) to U.S. Provisional Application No. 63 / 565,596, filed on March 15, 2024, the entire contents of which are incorporated herein by reference. Technical Field

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

[0004] For various reasons, optoelectronic devices utilizing organic materials are becoming increasingly popular. Many of the materials used to manufacture the devices are relatively inexpensive, so organic optoelectronic devices have the potential to offer cost advantages over inorganic devices. In addition, the inherent properties of organic materials (e.g., their flexibility) can 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 have performance advantages over conventional materials.

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

[0006] One application of emissive molecules is full-color displays. Industry standards for such displays require pixels adapted to emit specific colors (called "saturated" colors). Specifically, these standards require saturated red, green, and blue pixels. 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 emissions. The same technology can also be used for OLEDs. White OLEDs can be single-emission layer (EML) devices or stacked structures. Color can be measured using CIE coordinates, which are well known in the art. Summary of the Invention

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

[0008]

[0009] wherein the moiety A 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;

[0010] wherein moiety B is a polycyclic fused ring system consisting of at least five 5-membered or 6-membered carbocyclic or heterocyclic rings, at least one of which is a 5-membered ring;

[0011] wherein the at least one 5-membered ring of portion B comprises ring atoms selected from the group consisting of C, N, O, Si, S, Se, and Ge; the at least one 5-membered ring of portion B is fused to exactly one other ring; and the at least one 5-membered ring of portion B is not joined to M by a direct bond;

[0012] where Z 1 -Z 4 are each independently C or N;

[0013] Among them L 1 Selected from the group consisting of: direct bond, O, S, Se, NR, BR, BRR', PR, CR, C=O, C=NR, C=CRR', C=S, CRR', SO, SO2, P(O)R, SiRR', and GeRR';

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

[0015] where R A and R B Each independently represents monosubstituted to the maximum permissible substitution, or no substitution;

[0016] in represents a single bond or a double bond;

[0017] Where each R, R', R α 、R β 、R A and R B is independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, germanyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof;

[0018] Among them L A Coordinate with metal M;

[0019] wherein the metal M is selected from the group consisting of Ir, Rh, Re, Ru, Os, Pt, Pd, Ag, Au and Cu;

[0020] Wherein M can coordinate with other ligands;

[0021] Among them L A can be joined with other ligands to form tridentate, tetradentate, pentadentate, or hexadentate ligands; and

[0022] Any two substituents may be joined or fused to form a ring.

[0023] In another aspect, the present disclosure provides a formulation of a compound as described herein.

[0024] In yet another aspect, the present disclosure provides an OLED having an organic layer comprising a compound as described herein.

[0025] In yet another aspect, the present disclosure provides a consumer product comprising an OLED having an organic layer comprising a compound as described herein. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 An organic light-emitting device is shown.

[0027] Figure 2 An inverted organic light-emitting device without a separate electron transport layer is demonstrated. DETAILED DESCRIPTION

[0028] A. Terminology

[0029] Unless otherwise specified, the following terms used herein are defined as follows:

[0030] As used herein, "top" means farthest from the substrate, while "bottom" means closest to the substrate. When a first layer is described as being "disposed above" a second layer, the first layer is disposed farther from the substrate. Unless it is specified that the first layer is "in contact with" the second layer, other layers may be present between the first and second layers. For example, the cathode may be described as being "disposed above" the anode even if various organic layers are present between the cathode and the anode.

[0031] As used herein, "solution processable" means capable of being dissolved, dispersed, or transported in and / or deposited from a liquid medium in the form of a solution or suspension.

[0032] As used herein, and as will be generally understood by one skilled in the art, a first "highest occupied molecular orbital" (HOMO) or "lowest unoccupied molecular orbital" (LUMO) energy level is "greater than" or "higher than" a second HOMO or LUMO energy level if the first energy level is closer to the vacuum energy level. Since ionization potential (IP) is measured as negative energy relative to the vacuum energy level, a higher HOMO energy level corresponds to an IP with a smaller absolute value (a less negative IP). Similarly, a higher LUMO energy level corresponds to an electron affinity (EA) with a smaller absolute value (a less negative EA). On a conventional energy level diagram with the vacuum energy level at the top, the LUMO energy level of a material is higher than the HOMO energy level of the same material. A "higher" HOMO or LUMO energy level appears closer to the top of this diagram than a "lower" HOMO or LUMO energy level.

[0033] As used herein, and as will generally be understood by those skilled in the art, a first work function is "greater than" or "higher than" a second work function if the first work function has a higher absolute value. Because work functions are typically measured as negative numbers relative to the vacuum level, this means that a "higher" work function is more negative. On a conventional energy level diagram with the vacuum level at the top, a "higher" work function is illustrated as being further away from the vacuum level in a downward direction. Therefore, the definitions of HOMO and LUMO energy levels follow different rules than those for work functions.

[0034] Layers, materials, regions, and devices may be described herein with reference to the color of light they emit. Generally, as used herein, an emissive region described as producing a particular color of light may include one or more emissive layers disposed above one another in a stacked manner.

[0035] As used herein, a "NIR," "red," "green," "blue," or "yellow" layer, material, region, or device refers to a layer, material, region, or device that emits light in the wavelength ranges of approximately 700-1500 nm, 580-700 nm, 500-600 nm, 400-500 nm, or 540-600 nm, respectively, or a layer, material, region, or device having 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, a "deep blue" emission component refers to an emission having a peak emission wavelength that is at least about 4 nm less than the peak emission wavelength of a "light blue" emission component. Typically, the peak emission wavelength of the "light blue" emission component is in the range of approximately 465-500 nm, and the peak emission wavelength of the "deep blue" emission component is in the range of approximately 400-470 nm, but these ranges may vary for some configurations.

[0036] In some arrangements, a color-changing layer is provided that converts, modifies, or changes the color of light emitted by another layer to an emission having a different wavelength. This color-changing layer can be formulated to shift the wavelength of light emitted by another layer by a defined amount, as measured by the difference between the wavelength of the emitted light and the wavelength of the resulting light. Generally speaking, there are two types of color-changing layers: color filters that modify the spectrum by removing light of undesirable wavelengths, and color-changing layers that convert higher energy photons into lower energies. For example, there may be a "red" filter to filter the input light to remove light with wavelengths outside the range of approximately 580-700nm. A component of "color" refers to a component that, when activated or used, produces or otherwise emits light having 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, when activated within the device, emit two different colors as previously described.

[0037] As used herein, emissive materials, layers, and regions can be distinguished from each other and from other structures based on the light that the material, layer, or region initially produces, as opposed to the light that the same or different structure ultimately emits. Initial light production is typically the result of a change in energy levels that results in the emission of a photon. For example, an organic emissive material can initially produce blue light, which can be converted to red or green light by a color filter, quantum dots, or other structure, such that the complete emissive stack or sub-pixel emits red or green light. In this case, the initial emissive material, region, or layer can be referred to as the "blue" component, even if the sub-pixel is the "red" or "green" component.

[0038] In some cases, it may be preferable to describe the color of a component, such as the color of an emitting region, a sub-pixel, a color-changing layer, etc., in terms of 1931 CIE coordinates. For example, a yellow emitting material may have multiple peak emission wavelengths, one in or near the edge of the "green" region and one in or near the edge of the "red" region, as previously described. Thus, as used herein, each color term also corresponds to a shape in the 1931 CIE coordinate color space. Shapes in the 1931 CIE color space are constructed by tracing the trajectory between two color points and any other interior points. For example, the interior shape parameters for red, green, blue, and yellow may be defined as follows:

[0039]

[0040] The terms "halo," "halogen," and "halo" are used interchangeably and refer to fluorine, chlorine, bromine, and iodine.

[0041] The term "acyl" refers to a substituted carbonyl (-C(O)-R s ).

[0042] The term "ester" refers to a substituted oxycarbonyl (-OC(O)-R s OR-C(O)-OR s ) group.

[0043] The term "ether" refers to -OR s group.

[0044] The terms "thio" or "thioether" are used interchangeably and refer to -SR s group.

[0045] The term "selenoalkyl" refers to -SeR s group.

[0046] The term "sulfinyl" refers to -S(O)-R s group.

[0047] The term "sulfonyl" refers to -SO2-R s group.

[0048] The term "phosphino" refers to a group containing at least one phosphorus atom bonded to a related structure. Common examples of phosphino groups include, but are not limited to, -P(R s )2 group or -PO(R s )2 groups, wherein each R s Can be the same or different.

[0049] The term "silyl group" refers to a group containing at least one silicon atom bonded to the structure of interest. Common examples of silyl groups include, but are not limited to, -Si(R s)3 groups, wherein each R s Can be the same or different.

[0050] The term "germanyl" refers to a group containing at least one germanium atom bonded to a related structure. Common examples of germanyl groups include, but are not limited to, -Ge(R s )3 groups, wherein each R s Can be the same or different.

[0051] The term "boryl" refers to a group containing at least one boron atom bonded to a related structure. Common examples of boryl groups include, but are not limited to, -B(R s )2 group or its Lewis adduct -B(R s )3 groups, wherein R s Can be the same or different.

[0052] In each of the above, R s It can be hydrogen or a substituent selected from the group consisting of general substituents as defined in this application. s is selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, and combinations thereof. More preferably, R s Selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0053] 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 those containing 1 to 15 carbon atoms, preferably 1 to 9 carbon atoms, and include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1,3-dimethylpropyl, 1,1-dimethylpropyl, 2-ethylpropyl, 1,2-dimethylpropyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, n-heptyl, 2-methylhexyl, 3-methylhexyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl, 3,3-dimethylpentyl, 3-ethylpentyl, 2,2,3-trimethylbutyl, and the like. In addition, the alkyl group may be further substituted.

[0054] The term "cycloalkyl" refers to and includes monocyclic, polycyclic, and spirocyclic alkyl groups having cycloalkyl carbon atoms bonded to the relevant structure. Preferred cycloalkyl groups are those containing 3 to 12 ring carbon atoms and include cyclopropyl, cyclopentyl, cyclohexyl, bicyclo[3.1.1]heptyl, spiro[4.5]decyl, spiro[5.5]undecyl, adamantyl, and the like. In addition, the cycloalkyl group may be further substituted.

[0055] The term "heteroalkyl" or "heterocycloalkyl" refers to an alkyl or cycloalkyl group, respectively, having at least one carbon atom replaced by a heteroatom. Optionally, the at least one heteroatom is selected from O, S, N, P, B, Si, Ge, and Se, preferably O, S, or N. In addition, the heteroalkyl or heterocycloalkyl group may be further substituted.

[0056] The term "alkenyl" refers to and includes both straight-chain and branched alkene groups. Alkenyl groups are generally alkyl groups that include at least one carbon-carbon double bond in the alkyl chain, wherein one carbon atom is from a carbon-carbon double bond bonded to a related structure. Cycloalkenyl groups are generally cycloalkyl groups that include at least one carbon-carbon double bond in the cycloalkyl ring. As used herein, the term "heteroalkenyl" refers to an alkenyl group having at least one carbon atom replaced by a heteroatom. Optionally, at least one heteroatom is selected from O, S, N, P, B, Si, Ge, and Se, preferably O, S, or N. Preferred alkenyl, cycloalkenyl, or heteroalkenyl groups are those containing two to fifteen carbon atoms. In addition, the alkenyl, cycloalkenyl, or heteroalkenyl groups may be further substituted.

[0057] The term "alkynyl" refers to and includes both straight-chain and branched alkyne groups. Alkynyl groups are essentially alkyl groups that include at least one carbon-carbon triple bond in the alkyl chain, wherein one carbon atom is derived from a carbon-carbon triple bond bonded to a related structure. Preferred alkynyl groups are those containing from two to fifteen carbon atoms. In addition, alkynyl groups may be further substituted.

[0058] The terms "aralkyl" or "arylalkyl" are used interchangeably and refer to an alkyl group substituted with an aryl group bonded to an alkyl carbon atom of the associated structure. Additionally, the aralkyl group may be further substituted.

[0059] The term "heterocyclic group" refers to and includes 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 can be used interchangeably with heteroaryl groups. Preferred non-aromatic heterocyclic groups are non-aromatic heterocyclic groups containing 3 to 10 ring atoms, preferably non-aromatic heterocyclic groups containing 3 to 7 ring atoms including at least one heteroatom, and include cyclic amines such as morpholinyl, piperidinyl, pyrrolidinyl, and cyclic ethers / thioethers such as tetrahydrofuran, tetrahydropyran, tetrahydrothiophene, and the like. In addition, the heterocyclic group may be further substituted or fused.

[0060] The term "aryl" refers to and includes both monocyclic and polycyclic aromatic hydrocarbon groups. Polycyclic rings can have two or more rings in which two carbon atoms are common to two adjacent rings (the rings are "fused"). Preferred aryl groups are those containing six to thirty carbon atoms, preferably six to twenty-four carbon atoms, six to eighteen carbon atoms, and more preferably six to twelve carbon atoms. Especially preferred are aryl groups with six carbons, ten carbons, twelve carbons, fourteen carbons, or eighteen carbons. Suitable aryl groups include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenanthren, pyrene, Perylene and azulene, preferably phenyl, biphenyl, terphenyl, triphenylene and naphthalene. In addition, the aryl group may be further substituted or fused, such as but not limited to fluorene.

[0061] The term "heteroaryl" refers to and includes both monocyclic aromatic groups and polycyclic aromatic ring systems having at least one heteroatom. Heteroatoms include, but are not limited to, O, S, Se, N, P, B, Si, Ge, and Se. In many cases, O, S, N, or B are preferred heteroatoms. Monocyclic heteroaromatic systems are preferably monocyclic rings having 5 or 6 ring atoms, and the rings may have from one to six heteroatoms. Polycyclic heteroaromatic ring systems may have two or more aromatic rings in which two atoms are common to two adjacent rings (the rings are "fused"), wherein at least one of the rings is a heteroaryl. Polycyclic heteroaromatic ring systems may have from one to six heteroatoms in each ring of the polycyclic aromatic ring system. Preferred heteroaryl groups are those containing from three to thirty carbon atoms, preferably from three to twenty-four carbon atoms, from three to eighteen carbon atoms, and more preferably from three to twelve carbon atoms. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, Indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, selenophenodipyridine, azaborane, borazine, 5λ 2 ,9λ 2 -diaza-13b-borazinnaphtho[2,3,4-de]anthracene, 5λ 2-benzo[d]benzo[4,5]imidazo[3,2-a]imidazole and 5,9-dioxa-13b-borazinnaphtho[3,2,1-de]anthracene; preferably dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 5λ 2 ,9λ 2 -diaza-13b-borazinnaphtho[2,3,4-de]anthracene, 5λ 2 -benzo[d]benzo[4,5]imidazo[3,2-a]imidazole and 5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene. In addition, the heteroaryl group may be further substituted or fused.

[0062] 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-borazinnaphtho[2,3,4-de]anthracene, 5λ 2 Of particular interest are the benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, 5,9-dioxa-13b-borazinonaphtho[3,2,1-de]anthracene groups, and the corresponding aza analogs of each.

[0063] In many cases, the universal substituents are selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, germanyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, selenoalkyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

[0064] In some cases, preferred universal substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silanyl, germanyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thio, and combinations thereof.

[0065] In some cases, more preferred universal substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, alkoxy, aryloxy, amino, silanyl, germanyl, borane, aryl, heteroaryl, nitrile, thio, and combinations thereof.

[0066] In some cases, even more preferred universal substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, silyl, aryl, heteroaryl, nitrile, and combinations thereof.

[0067] In still other cases, the most preferred universal substituents are selected from the group consisting of deuterium, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0068] 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 it represents a single substitution, one R 1 must not be H (i.e., substituted). Similarly, when R 1 When it represents disubstituted, the two R 1 must not be H. Similarly, when R 1 When it represents zero or no substitution, R 1 For example, it can be hydrogen for all available valences of the ring atoms, such as the carbon atoms in benzene and the nitrogen atoms in pyrrole, or simply none for ring atoms with fully saturated valences, such as the nitrogen atoms in pyridine. The maximum number of substitutions possible in the ring structure will depend on the total number of available valences among the ring atoms.

[0069] As used herein, "combinations thereof" means that one or more members of the applicable list are combined to form a known or chemically stable arrangement that a person of ordinary skill in the art can conceive from the applicable list. For example, an alkyl group and a deuterium group can be combined to form a partially or fully deuterated alkyl group; a halogen and an alkyl group can be combined to form a haloalkyl substituent; and a halogen, an alkyl group, and an aryl group can be combined to form a haloaralkyl group. In one example, the term substituted includes a combination of two to four of the listed groups. In another example, the term substituted includes a combination of two to three groups. In yet another example, the term substituted includes a combination of two groups. Preferred combinations of substituents are combinations containing up to fifty atoms that are not hydrogen or deuterium, or combinations that include up to forty atoms that are not hydrogen or deuterium, or combinations that include 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.

[0070] The "aza" designation in the fragments described herein, i.e., aza-dibenzofuran, aza-dibenzothiophene, etc., means that one or more of the CH groups in the corresponding aromatic ring can be replaced by a nitrogen atom, for example, and without limitation, azatriphenylene encompasses dibenzo[f,h]quinoxaline and dibenzo[f,h]quinoline. One of ordinary skill in the art can readily envision other nitrogen analogs of the aza-derivatives described above, and all such analogs are intended to be encompassed by the term as set forth herein.

[0071] As used herein, " deuterium " refers to an isotope of hydrogen. Deuterated compounds can be easily 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. With further reference to Ming Yan et al., Tetrahedron 2015, 71, 1425-30 and Atzrodt et al., Angew. Chem. Int. Ed. (Review) 2007, 46, 7744-65 (which are incorporated by reference in their entirety) describe the deuteration of methylene hydrogen in benzylamine and an effective way to replace aromatic ring hydrogen with deuterium.

[0072] As used herein, any specific listed substituent, such as but not limited to methyl, phenyl, pyridyl, etc., includes its non-deuterated, partially deuterated, and fully deuterated forms. Similarly, substituents such as but not limited to alkyl, aryl, cycloalkyl, heteroaryl, etc., also include their non-deuterated, partially deuterated, and fully deuterated forms. Unless otherwise specified, atoms in a chemical structure that do not have a valence fully filled by H or D should be considered to include their non-deuterated, partially deuterated, and fully deuterated forms. For example, the chemical structure This is meant to include C6H6, C6D6, C6H3D3 and any other partially deuterated variants thereof. Some common basic partially or fully deuterated groups include, but are not limited to, CD3, CD2C(CH3)3, C(CD3)3 and C6D5.

[0073] It should be understood that when a molecular fragment is described as a substituent or otherwise attached to another moiety, its name can be written as if it is a fragment (e.g., phenyl, phenylene, naphthyl, dibenzofuranyl) or as if it is an entire molecule (e.g., benzene, naphthalene, dibenzofuran). As used herein, these different ways of naming substituents or attaching fragments are considered equivalent.

[0074] In some cases, a pair of substituents in a molecule can be optionally joined or fused to form a ring. Preferred rings are five- to nine-membered carbocyclic or heterocyclic rings, including two cases where the portion of the ring formed by the pair of substituents is saturated and the portion of the ring formed by the pair of substituents is unsaturated. In other cases, a pair of adjacent substituents can be optionally joined or fused to form a ring. As used herein, "adjacent" means that the two substituents involved can be immediately adjacent to each other on the same ring, or on two adjacent rings with two closest available substitutable positions (such as the 2, 2' positions in biphenyl or the 1, 8 positions in naphthalene).

[0075] B. Compounds of the Disclosure

[0076] In one aspect, the present disclosure provides a compound having a first ligand L comprising a structure of Formula I A :

[0077]

[0078] wherein the moiety A 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;

[0079] wherein moiety B is a polycyclic fused ring system consisting of at least five 5-membered or 6-membered carbocyclic or heterocyclic rings, at least one of which is a 5-membered ring;

[0080] wherein the at least one 5-membered ring of portion B comprises ring atoms selected from the group consisting of C, N, O, Si, S, Se, and Ge; the at least one 5-membered ring of portion B is fused to exactly one other ring; and the at least one 5-membered ring of portion B is not joined to M by a direct bond;

[0081] where Z 1 -Z 4 are each independently C or N;

[0082] Among them L 1 Selected from the group consisting of: direct bond, O, S, Se, NR, BR, BRR', PR, CR, C=O, C=NR, C=CRR', C=S, CRR', SO, SO2, P(O)R, SiRR', and GeRR';

[0083] where K 1 and K 2 Each independently selected from the group consisting of: direct bond, O, S, N (R α )、P(R α )、B(R α )、C(R α )(R β ) and Si(R α )(R β );

[0084] where R A and R B Each independently represents monosubstituted to the maximum permissible substitution, or no substitution;

[0085] in represents a single bond or a double bond;

[0086] Where each R, R', R α 、R β 、R A and RB is independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, germanyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof;

[0087] Among them L A Coordinate with metal M;

[0088] wherein the metal M is selected from the group consisting of Ir, Rh, Re, Ru, Os, Pt, Pd, Ag, Au and Cu;

[0089] Wherein M can coordinate with other ligands;

[0090] Among them L A can be joined with other ligands to form tridentate, tetradentate, pentadentate, or hexadentate ligands; and

[0091] Any two substituents may be joined or fused to form a ring.

[0092] In some embodiments, the first ligand L A Consisting essentially of Formula I.

[0093] In some embodiments, the first ligand L A It has the structure of formula I.

[0094] In some embodiments, R, R', R α 、R β 、R A and R B Each of the groups is independently hydrogen or a substituent selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silanyl, germanyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thio, and combinations thereof.

[0095] In some embodiments, L 1 It is a direct key.

[0096] In some embodiments, L 1 Selected from the group consisting of: O, S, Se, NR, BR, BRR', PR, CR, C=O, C=NR, C=CRR', C=S, CRR', SO, SO2, P(O)R, SiRR', and GeRR';

[0097] In some embodiments, Z 1 -Z 4 At least one of them is N.

[0098] In some embodiments, Z 1 -Z 4 Exactly one of them is N.

[0099] In some embodiments, Z 1 It's N.

[0100] In some embodiments, Z 1 is N and Z 2 It’s C.

[0101] In some embodiments, Z 1 is neutral N and Z 2 It is anion C.

[0102] In some embodiments, Z 1 is a neutral carbene C and Z 2 It is anion C.

[0103] In some embodiments, Z 2 It's N.

[0104] In some embodiments, Z 2 is N and Z 1 It’s C.

[0105] In some embodiments, Z 3 and Z 4 One of them is N.

[0106] In some embodiments, K 1 and K 2 One of them is a direct key.

[0107] In some embodiments, K 1 and K 2 One selected from O, S, N (R α )、P(R α )、B(R α )、C(R α )(R β ) and Si(R α )(R β )

[0108] In some embodiments, moiety A comprises a 6-membered ring.

[0109] In some embodiments, moiety A comprises a 6-membered aromatic ring.

[0110] In some embodiments, moiety A comprises a 6-membered carbocyclic aromatic ring.

[0111] In some embodiments, moiety A comprises a 6-membered heterocyclic aromatic ring.

[0112] In some embodiments, moiety A comprises a 5-membered ring.

[0113] In some embodiments, moiety A comprises a 5-membered aromatic ring.

[0114] In some embodiments, moiety A comprises a 5-membered heterocyclic aromatic ring.

[0115] In some embodiments, moiety A comprises a 5-membered ring and a 6-membered ring.

[0116] In some embodiments, moiety A comprises a 5-membered ring and a 6-membered ring, wherein the 5-membered ring is coordinated to the metal M.

[0117] In some embodiments, moiety A is a 6-membered ring.

[0118] In some embodiments, moiety A is a 6-membered aromatic ring.

[0119] In some embodiments, moiety A is a 6-membered carbocyclic aromatic ring.

[0120] In some embodiments, moiety A is a 6-membered heterocyclic aromatic ring.

[0121] In some embodiments, moiety B comprises exactly five fused 5- or 6-membered rings.

[0122] In some embodiments, moiety B is fully aromatic.

[0123] In some embodiments, moiety B comprises at least one non-aromatic ring.

[0124] In some embodiments, moiety B comprises at least one non-aromatic 5-membered ring.

[0125] In some embodiments, moiety B comprises at least one non-aromatic 5-membered carbocyclic ring.

[0126] In some embodiments, moiety B comprises at least two 5-membered rings.

[0127] In some embodiments, moiety B comprises at least two 5-membered heterocyclic rings.

[0128] In some embodiments, moiety B comprises exactly two 5-membered rings.

[0129] In some embodiments, moiety B comprises exactly two 5-membered heterocyclic rings.

[0130] In some embodiments, moiety B comprises at least three 5-membered rings.

[0131] In some embodiments, moiety B comprises at least three 5-membered heterocyclic rings.

[0132] In some embodiments, moiety B comprises at least two 6-membered rings.

[0133] In some embodiments, moiety B comprises at least two 6-membered carbon rings.

[0134] In some embodiments, moiety B comprises a 6-membered ring directly fused to three other 5- or 6-membered rings.

[0135] In some embodiments, moiety B comprises at least three 6-membered heterocyclic rings.

[0136] In some embodiments, moiety B comprises at least one 5- or 6-membered heterocyclic ring comprising at least two different heteroatoms.

[0137] In some embodiments, moiety B comprises at least one 5- or 6-membered heterocyclic ring comprising exactly two different heteroatoms.

[0138] In some embodiments, moiety B comprises at least one 5- or 6-membered heterocyclic ring comprising one N atom and one O atom.

[0139] In some embodiments, moiety B comprises at least one 5- or 6-membered heterocyclic ring comprising one N atom and one S atom.

[0140] In some embodiments, moiety B comprises at least one 5-membered heterocyclic ring comprising at least two different heteroatoms.

[0141] In some embodiments, moiety B comprises at least one 5-membered heterocyclic ring comprising exactly two different heteroatoms.

[0142] In some embodiments, moiety B comprises at least one 5-membered heterocyclic ring comprising one N atom and one O atom.

[0143] In some embodiments, moiety B comprises at least one 5- or 6-membered heterocyclic ring comprising one N atom and one S atom.

[0144] In some embodiments, moiety B comprises at least one 5-membered ring comprising an S atom.

[0145] In some embodiments, moiety B comprises at least two 5-membered rings comprising S atoms.

[0146] In some embodiments, moiety B comprises at least one 5-membered carbocyclic ring.

[0147] In some embodiments, moiety B comprises at least one 5-membered carbocyclic non-aromatic ring.

[0148] In some embodiments, M is Ir.

[0149] In some embodiments, M is Pt.

[0150] In some embodiments, M is Pd.

[0151] In some embodiments, the first ligand L A Contains at least one isopropyl or tert-butyl group.

[0152] In some embodiments, the first ligand L A Contains at least two isopropyl or tert-butyl groups.

[0153] In some embodiments, each ring in moiety A and moiety B can be independently selected from the group consisting of benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, imidazole-derived carbene, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole, triazole, naphthalene, quinoline, isoquinoline, quinazoline, benzofuran, aza-benzofuran, benzoxazole, aza-benzoxazole, benzothiophene, aza-benzothiophene, benzothiazole, Aza-benzothiazole, benzoselenophene, aza-benzoselenophene, indene, aza-indene, indole, aza-indole, benzimidazole, aza-benzimidazole, benzimidazole-derived carbene, aza-benzimidazole-derived carbene, carbazole, aza-carbazole, dibenzofuran, aza-dibenzofuran, dibenzothiophene, aza-dibenzothiophene, quinoxaline, phthalazine, phenanthrene, aza-phenanthrene, anthracene, aza-anthracene, phenanthridine, fluorene, and aza-fluorene.

[0154] In some embodiments, the first ligand L A In some embodiments, the electron-withdrawing group has a Hammett constant greater than 0. In some embodiments, the electron-withdrawing group has a Hammett constant equal to or greater than 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, or 1.1.

[0155] In some embodiments, the first ligand L A comprising an electron withdrawing group selected from the group consisting of: F, CF3, CN, COCH3, CHO, COCF3, COOMe, COOCF3, NO2, SF3, SiF3, PF4, SF5, OCF3, SCF3, SeCF3, SOCF3, SeOCF3, SO2F, SO2CF3, SeO2CF3, OSeO2CF3, OCN, SCN, SeCN, NC, + N(R k2 )3、(R k2 )2CCN、(R k2 )2CCF3、CNC(CF3)2、BR k3 R k2, substituted or unsubstituted dibenzoborole, 1-substituted carbazole, 1,9-substituted carbazole, substituted or unsubstituted carbazole, substituted or unsubstituted pyridine, substituted or unsubstituted pyrimidine, substituted or unsubstituted pyrazine, substituted or unsubstituted pyridoxine, substituted or unsubstituted triazine, substituted or unsubstituted oxazole, substituted or unsubstituted benzoxazole, substituted or unsubstituted thiazole, substituted or unsubstituted benzothiazole, substituted or unsubstituted imidazole, substituted or unsubstituted benzimidazole, ketone, carboxylic acid, ester, nitrile, isonitrile, sulfinyl, sulfonyl, partially and fully fluorinated alkyl groups, partially and fully fluorinated aryl groups, partially and fully fluorinated heteroaryl groups, cyano-containing alkyl groups, cyano-containing aryl groups, cyano-containing heteroaryl groups, isocyanate,

[0156]

[0157] Each R k1 indicates monosubstituted to the maximum permissible substitution, or no substitution;

[0158] where Y G Select from the group consisting of: BR e NR e PR e ,O,S,Se,C=O,S=O,SO2,CR e R f 、SiR e R f and GeR e R f ;and

[0159] R k1 、R k2 、R k3 、R e and R f Each of is independently hydrogen or a substituent selected from the group consisting of general substituents defined herein.

[0160] In some embodiments, the first ligand L A comprising an electron withdrawing group selected from the group consisting of the following structures in the EWG2 list:

[0161]

[0162]

[0163]

[0164] In some embodiments, the first ligand L Acomprising an electron withdrawing group selected from the group consisting of the structures in the following EWG3 list:

[0165]

[0166] In some embodiments, the first ligand L A comprising an electron withdrawing group selected from the group consisting of the following structures in the EWG4 list:

[0167] In some embodiments, the first ligand L A comprising an electron-withdrawing group, wherein the electron-withdrawing group is a π-electron-deficient electron-withdrawing group. In some embodiments, the π-electron-deficient electron-withdrawing group is selected from the group consisting of the structures listed in the following π-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 dibenzoborole, 1-substituted carbazole, 1,9-substituted carbazole, substituted or unsubstituted carbazole, substituted or unsubstituted pyridine, substituted or unsubstituted pyrimidine, substituted or unsubstituted pyrazine, substituted or unsubstituted pyridazine, substituted or unsubstituted triazine, substituted or unsubstituted oxazole, substituted or unsubstituted benzoxazole, substituted or unsubstituted thiazole, substituted or unsubstituted benzothiazole, substituted or unsubstituted imidazole, substituted or unsubstituted benzimidazole, ketone, carboxylic acid, ester, nitrile, isonitrile, sulfinyl, sulfonyl, partially and fully fluorinated aryl, partially and fully fluorinated heteroaryl, cyano-containing aryl, cyano-containing heteroaryl, isocyanate, where the variables are the same as defined previously.

[0168] In some embodiments, the first ligand L A comprises an electron withdrawing group from the EWG1 list as defined herein. In some embodiments, the first ligand L A comprises an electron withdrawing group from the EWG2 list as defined herein. In some embodiments, the first ligand L Acomprises an electron withdrawing group from the EWG3 list as defined herein. In some embodiments, the first ligand L A comprises an electron withdrawing group from the EWG4 list as defined herein. In some embodiments, the first ligand L A Electron withdrawing groups from the π-EWG list as defined herein are included.

[0169] In some embodiments, at least one R A is or comprises an electron withdrawing group. In some embodiments, at least one R A is or comprises an electron withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R A is or comprises an electron withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R A is or comprises an electron withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R A is or comprises an electron withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R A is or comprises an electron withdrawing group from the π-EWG list as defined herein.

[0170] In some embodiments, at least one R B is or comprises an electron withdrawing group. In some embodiments, at least one R B is or comprises an electron withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R B is or comprises an electron withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R B is or comprises an electron withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R B is or comprises an electron withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R B is or comprises an electron withdrawing group from the π-EWG list as defined herein.

[0171] In some embodiments, at least one of R or R' is or comprises an electron withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one of R or R' is or comprises an electron withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one of R or R' is or comprises an electron withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one of R or R' is or comprises an electron withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one of R or R' is or comprises an electron withdrawing group from the π-EWG list as defined herein.

[0172] In some embodiments, the first ligand L A Selected from the group consisting of the following structures defined in Listing 1 below:

[0173]

[0174]

[0175]

[0176]

[0177]

[0178]

[0179]

[0180] wherein each of Y1-Y5 is independently selected from the group consisting of O, S, Se, NR, BR, BRR', PR, CR, C=O, C=NR, C=CRR', C=S, CRR', SO, SO2, P(O)R, SiRR', and GeRR';

[0181] X1-X 14 Each of is independently C or N;

[0182] The remaining variables are the same as defined previously; and

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

[0184] In some embodiments, X1-X 14 All are C. In some embodiments, X1-X 14 At least one of X1-X is N. In some embodiments, X1-X 14 At least two of X1-X1 are N. In some embodiments, 14In some embodiments, at least three of X are N. In some embodiments, X3 is N. In some embodiments, X4 is N. In some embodiments, X5 is N. In some embodiments, X6 is N. In some embodiments, X7 is N. In some embodiments, X8 is N. In some embodiments, Y1 is O. In some embodiments, Y2 is O. In some embodiments, Y3 is O. In some embodiments, Y4 is O. In some embodiments, Y5 is O.

[0185] In the first ligand L A In some embodiments selected from List 1, R, R', R A or R B In some embodiments, at least one R A is partially or fully deuterated. In some embodiments, at least one R B is partially or fully deuterated.

[0186] In the first ligand L A In some embodiments selected from List 1, at least one R A is or comprises an electron withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R A is or comprises an electron withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R A is or comprises an electron withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R A is or comprises an electron withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R AA is or comprises an electron withdrawing group from the π-EWG list as defined herein.

[0187] In the first ligand L A In some embodiments selected from List 1, at least one R B is or comprises an electron withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R B is or comprises an electron withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R B is or comprises an electron withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R B is or comprises an electron withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R B is or comprises an electron withdrawing group from the π-EWG list as defined herein.

[0188] In some embodiments, the first ligand LA Selected from the group consisting of the following structures defined in Listing 2 below:

[0189]

[0190]

[0191]

[0192]

[0193]

[0194]

[0195]

[0196]

[0197]

[0198]

[0199] in

[0200] R AA and R BB Each independently represents monosubstituted to the maximum permissible substitution, or no substitution;

[0201] Each R AA and R BB are independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, germanyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof; and

[0202] Any two substituents may be optionally joined or fused to form a ring.

[0203] In the first ligand L A In some embodiments selected from Listing 2, R AA or R BB In some embodiments, at least one R AA is partially or fully deuterated. In some embodiments, at least one R BB is partially or fully deuterated.

[0204] In the first ligand L A In some embodiments selected from List 2, at least one RAA is or comprises an electron withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R AA is or comprises an electron withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R AA is or comprises an electron withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R AA is or comprises an electron withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R AA is or comprises an electron withdrawing group from the π-EWG list as defined herein.

[0205] In the first ligand L A In some embodiments selected from List 2, at least one R BB is or comprises an electron withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R BB is or comprises an electron withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R BB is or comprises an electron withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R BB is or comprises an electron withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R BB is or comprises an electron withdrawing group from the π-EWG list as defined herein.

[0206] In some embodiments, the first L A Selected from the group consisting of: L Ai (R J )(R K )(R L )(Y M ), where i is an integer from 1 to 111, R J 、R K and R L Each of is independently selected from V1 to V148; and Y M selected from Y1 to R12; and L A 1-(V1)(V1)(V1)(Y1) to L A 111-(V148)(V148)(V148)(Y12), and L A 1-(R1)(R1)(R1)(Y1) to L A Each of 111-(V148)(V148)(V148)(Y12) is defined in Listing 3 below:

[0207]

[0208]

[0209]

[0210]

[0211]

[0212]

[0213]

[0214]

[0215]

[0216] Where V1 to V148 have the following structure as defined in Listing 7 below:

[0217]

[0218]

[0219]

[0220] where Y1 to Y12 have the following structure

[0221]

[0222] In some embodiments, the compound has M(L A ) p (L B ) q (L C ) r The formula, where L B and L C Each is a bidentate ligand; and wherein p is 1, 2, or 3; q is 0, 1, or 2; r is 0, 1, or 2; and p+q+r is the oxidation state of the metal M.

[0223] In some embodiments, the compound has a formula selected from the group consisting of: Ir(L A )3、Ir(L A )(L B )2、Ir(L A )2(L B )、Ir(L A )2(L C ) and Ir(L A )(L B )(L C); and wherein L A , L B and L C Different from each other.

[0224] In some embodiments, L B is a substituted or unsubstituted phenylpyridine, and L C It is a substituted or unsubstituted acetylacetonate.

[0225] In some embodiments, the compound has the formula Pt(L A )(L B ); and wherein L A With L B Can be the same or different.

[0226] In some embodiments, L A With L B connected to form a tetradentate ligand.

[0227] In some embodiments, L B Include In some embodiments, Y 1 to Y 4 In some embodiments, each of Y is independently carbon. 1 to Y 4 At least one of is N. In some embodiments, Y 1 to Y 4 Exactly one of is N. In some embodiments, Y 1 is N. In some embodiments, Y 2 is N. In some embodiments, Y 3 is N. In some embodiments, Y 4 is N. In some embodiments, at least one R a is a tertiary alkyl, a silane or a germyl group. In some embodiments, at least one R a In some embodiments, Y 3 is C and connected to it R a is a tertiary alkyl, a silyl or a germanyl group. In some embodiments, Y 1 to Y 3 It's C, Y 4 is N, and with Y 3 Connected R a is a tertiary alkyl, a silyl or a germanyl group. In some embodiments, Y 1 to Y 3 It's C, Y 4 is N, and with Y 2 Connected R ais a tertiary alkyl, a silane or a germyl group. In some embodiments, at least one R b is a tertiary alkyl, a silyl or a germyl group. In some embodiments, the tertiary alkyl group is a tert-butyl group. In some embodiments, at least one pair of R a 、A pair of R b or a pair of R a and R b Join or condense into a ring.

[0228] In some embodiments, L B is selected from the group consisting of: a substituted or unsubstituted phenylpyridine, a substituted or unsubstituted phenylimidazole, and a substituted or unsubstituted phenylbenzimidazole; and L C is a substituted or unsubstituted acetylacetonate. In some embodiments, L B and L C Each independently selected from the group consisting of the following structures from Listing 4 below:

[0229]

[0230]

[0231]

[0232] in:

[0233] T is selected from the group consisting of B, Al, Ga and In;

[0234] K 1 'Selected from the group consisting of: single bond, O, S, NR e PR e BR e , CR e R f and SiR e R f ;

[0235] Y 1 to Y 13 Each of is independently selected from the group consisting of C and N;

[0236] 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、

[0237] C=S、C=Se、C=NR e 、C=CRe R f 、S=O、SO2、CR e R f 、SiR e R f and GeR e R f ;

[0238] R e and R f may be fused or joined to form a ring;

[0239] Each R a 、R b 、R c and R d independently represents monosubstitution to the maximum allowed number of substitutions, or no substitution;

[0240] R a1 、R b1 、R c1 、R d1 、R a 、R b 、R c 、R d 、R e and R f each of which is independently hydrogen or a substituent selected from the group consisting of deuterium, halo, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, germanyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, selenanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and

[0241] R a1 、R b1 、R c1 、R d1 、R a 、R b 、R c and R d Any two substituents of may be fused or joined to form a ring or to form a multidentate ligand.

[0242] In some embodiments, L B and L C Each independently selected from the group consisting of the following structures from Listing 5 below:

[0243]

[0244]

[0245]

[0246]

[0247]

[0248]

[0249]

[0250] where R a '、R b '、R c '、R d ' and R e ' Each independently represents zero substitution, monosubstitution, or up to the maximum allowed substitution on its associated ring;

[0251] Each R a '、R b '、R c '、R d ' and R e ' are each independently hydrogen or a substituent selected from the group consisting of deuterium, halo, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, germanyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, selenanyl, and combinations thereof; and

[0252] where R a '、R b '、R c '、R d ' and R e Two adjacent substituents of ' may be fused or joined to form a ring or to form a multidentate ligand.

[0253] In some embodiments, L A Can be selected from L Ai (R J )(R K )(R L )(Y M ), where i is an integer from 1 to 111; and L B Can be selected from L Bk , where k is an integer from 1 to 541,

[0254] in:

[0255] When the compound has the formula Ir(L Ai (R J )(R K )(R L )(Y M ))3, the compound is selected from Ir(LA 1-(V1)(V1)(V1)(Y1))3 to Ir(L A The group consisting of 111(V148)(V148)(V148)(Y12))3;

[0256] When the compound has the formula Ir(L Ai (R J )(R K )(R L )(Y M ))(L Bk )2, the compound is selected from Ir(L A 1-(V1)(V1)(V1)(Y1))(L B1 )2 to Ir(L A 111(V148)(V148)(V148)(Y12))(L B541 )2;

[0257] When the compound has the formula Ir(L Ai (R J )(R K )(R L )(Y M ))2(L Bk ), the compound is selected from Ir(L A 1-(V1)(V1)(V1)(Y1))2(L B1 ) to Ir(L A 111(V148)(V148)(V148)(Y12))2(L B541 )

[0258] When the compound has the formula Ir(L Ai (R J )(R K )(R L )(Y M ))2(L Cj-I ), the compound is selected from Ir(L A 1-(V1)(V1)(V1)(Y1))2(L C1-I ) to Ir(L A 111(V148)(V148)(V148)(Y12))2(L C1416-I ); and

[0259] When the compound has the formula Ir(L Ai (R J )(R K )(R L )(Y M ))2(LCj-II ), the compound is selected from Ir(L A 1-(V1)(V1)(V1)(Y1))2(L C1-II ) to Ir(L A 111(V148)(V148)(V148)(Y12))2(L C1416-II )

[0260] Each L Ai (R J )(R K )(R L )(Y M ) is as defined above;

[0261] Where k is an integer from 1 to 541, and each L Bk With the following structure defined in Listing 6:

[0262]

[0263]

[0264]

[0265]

[0266]

[0267]

[0268]

[0269]

[0270]

[0271]

[0272]

[0273]

[0274]

[0275]

[0276] Each L Cj-I Based on the formula structure; and

[0277] Each L Cj-II Based on the formula The structure of L Cj-I and L Cj-II Each L in Cj , R 201 and R 202 Each is independently defined in Table A below as follows:

[0278]

[0279]

[0280]

[0281]

[0282]

[0283]

[0284]

[0285]

[0286]

[0287]

[0288]

[0289] where R D1 to R D246 With the following structure in Listing 17:

[0290]

[0291]

[0292]

[0293]

[0294]

[0295] In some embodiments, the compound is selected from the group consisting of only L Bk The group consisting of those compounds corresponding to one of the following: L B1 、L B30 、L B31 、L B109 、L B110 、L B112 、L B113 、L B114 、LB125 、L B127 、L B138 、L B140 、L B149 、L B150 、L B170 、L B171 、L B172 、L B174 、L B208 、L B241 、L B312 、L B315 、L B356 、L B357 、L B367 、L B371 、L B382 、L B439 、L B440 、L B455 、L B456 、L B457 、L B458 、L B461 、L B462 、L B463 、L B469 and L B476 .

[0296] In some embodiments, the compound is selected from the group consisting of only L Bk The group consisting of those compounds corresponding to one of the following: L B1 、L B30 、L B31 、L B125 、L B138 、L B171 、L B172 、L B356 、L B357 、L B367 、L B371 、L B382 、L B455 and L B456 .

[0297] In some embodiments, the compound is selected from the group consisting of Cj-I or L Cj-II The group of compounds consisting of ligands corresponding to R 201 and R 202 is defined as one of the following structures: R D1 、R D3 、R D4 、R D5 、R D9 、R D10 、R D17 、R D18 、R D20、R D22 、R D37 、R D40 、R D41 、R D42 、R D43 、R D48 、R D49 、R D50 、R D54 、R D55 、R D58 、R D59 、R D78 、R D79 、R D81 、R D87 、R D88 、R D89 、R D93 、R D116 、R D117 、R D118 、R D119 、R D120 、R D133 、R D134 、R D135 、R D136 、R D143 、R D144 、R D145 、R D146 、R D147 、R D149 、R D151 、R D154 、R D155 、R D161 、R D175 R D190 、R D193 、R D200 、R D201 、R D206 、R D210 、R D214 、R D215 、R D216 、R D218 、R D219 、R D220 、R D227 、R D237 、R D241 、R D242 、R D245 and R D246 .

[0298] In some embodiments, the compound is selected from the group consisting of Cj-I or L Cj-II The group of compounds consisting of ligands whose corresponding R 201 and R 202is defined as one selected from the following structures: R D1 、R D3 、R D4 、R D5 、R D9 、R D10 、R D17 、R D22 、R D43 、R D50 、R D78 、R D116 、R D118 、R D133 、R D134 、R D135 、R D136 、R D143 、R D144 、R D145 、R D146 、R D149 、R D151 、R D154 、R D155 R D190 、R D193 、R D200 、R D201 、R D206 、R D210 、R D214 、R D215 、R D216 、R D218 、R D219 、R D220 、R D227 、R D237 、R D241 、R D242 、R D245 and R D246 .

[0299] In some embodiments, the compound is selected from the group consisting of only Cj-I The group consisting of those compounds whose ligand has one of the following structures as defined in List 8 below:

[0300]

[0301]

[0302] In some embodiments, L A Selected from the group consisting of the structures of List 1, List 2 and List 3. In some embodiments, L B Selected from the group consisting of the structures of Listing 4, Listing 5, and Listing 6. In some embodiments, L A Selected from L defined herein Ai (R J)(R K )(R L )(Y M ) of the structure of List 3, the L Ai (R J )(R K )(R L )(Y M ) by L A 1-(V1)(V1)(V1)(Y1) to L A 111-(V148)(V148)(V148)(Y12), and L B Selected from L as defined herein Bk The list consists of 6 groups, the L Bk By L B1 to L B541 composition.

[0303] In some embodiments, the compound may be Ir(L A )3、Ir(L A )2(L B )、Ir(L A )(L B )2、Ir(L A )2(L C )、Ir(L A )(L C )2 or Ir(L A )(L B )(L C ).

[0304] In some embodiments, the compound may be Ir(L A 1-(V1)(V1)(V1)(Y1))3 to

[0305] Ir(L A The compound composed of Ir(L Ai (R J )(R K )(R L )(Y M ))3、Ir(L Ai (R J )(R K )(R L )(Y M ))2(L B )、Ir(L Ai (R J )(R K )(R L )(Y M ))(LB )2、Ir(L A )2(L Bk )、Ir(L A )(L Bk )2、By Ir(L A 1-(V1)(V1)(V1)(Y1))2(L B1 ) to Ir(L A 111-(V148)(V148)(V148)(Y12))2(L B541 ) of compounds composed of Ir(L Ai (R J )(R K )(R L )(Y M ))2(L Bk ), by Ir(L A 1-(V1)(V1)(V1)(Y1))(L B1 )2 to Ir(L A 111-(V148)(V148)(V148)(Y12))(L B541 )2 compounds composed of Ir(L Ai (R J )(R K )(R L )(Y M ))(L Bk )2、By Ir(L A 1-(V1)(V1)(V1)(Y1))2(L C1-I )arrive

[0306] Ir(L A 111-(V148)(V148)(V148)(Y12))2(L C1416-I ) of compounds composed of Ir(L Ai (R J )(R K )(R L )(Y M ))2(L Cj-I ), by Ir(L A 1-(V1)(V1)(V1)(Y1))2(L C1-II )arrive

[0307] Ir(L A 111-(V148)(V148)(V148)(Y12))2(L C1416-II ) of compounds composed of Ir(L Ai (R J )(R K )(R L )(YM ))2(L Cj-II ), by Ir(L A 1-(V1)(V1)(V1)(Y1))(L B1 )(L C1-I )arrive

[0308] Ir(L A 111-(V148)(V148)(V148)(Y12))(L B541 )(L C1416-I ) of compounds composed of Ir(L Ai (R J )(R K )(R L )(Y M ))(L Bk )(L Cj-I ), or by Ir(L A 1-(V1)(V1)(V1)(Y1))(L B1 )(L C1-II ) to Ir(L A 111-(V148)(V148)(V148)(Y12))(L B541 )(L C1416-II ) of compounds composed of Ir(L Ai (R J )(R K )(R L )(Y M ))(L Bk )(L Cj-II ), where L Ai (R J )(R K )(R L )(Y M ), L Bk , L Cj-II and L Cj-II are defined in this article.

[0309] In some embodiments, the compound is selected from the group consisting of the structures in Listing 9 below:

[0310]

[0311]

[0312]

[0313]

[0314]

[0315]

[0316]

[0317]

[0318] In some embodiments, the compound comprises the structure of Formula II:

[0319]

[0320] in:

[0321] M 1 is Pd or Pt;

[0322] Moieties E and F are each independently a monocyclic or polycyclic fused ring system, wherein each ring in said monocyclic or polycyclic fused ring system is independently a 5- to 10-membered carbocyclic or heterocyclic ring;

[0323] Z 5 and Z 6 are each independently C or N;

[0324] K 1 , K 2 , K 3 and K 4 Each independently selected from the group consisting of: direct bond, O, S, N (R α )、P(R α )、B(R α )、C(R α )(R β ) and Si(R α )(R β ), wherein at least two of them are direct bonds;

[0325] L 2 , L 3 and L 4 Each independently absent or selected from the group consisting of a direct bond, BR, BRR', NR, PR, P(O)R, O, S, Se, C=O, C=S, C=Se, C=NR, C=CRR', S=O, SO2, CR, CRR', SiRR', GeRR', alkylene, cycloalkyl, aryl, cycloalkylene, arylene, heteroarylene, and combinations thereof, wherein L is present 3 and L 4 at least one of;

[0326] R E and R F Each independently represents zero substitution, monosubstitution, or up to the maximum allowed number of substitutions on its associated ring;

[0327] R α 、R β , R', R", R E and R F each of which is independently hydrogen or a substituent selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silanyl, germanyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thio, and combinations thereof;

[0328] Where chemically feasible, two adjacent R A 、R B 、R C 、R E and R F may be joined or fused together to form a ring; and

[0329] Z 1 -Z 4 、L 1 、R A 、R B , Part A and Part B are all defined the same as above.

[0330] In some embodiments of Formula II, R, R', R A 、R B 、R E or R F At least one of is partially or fully deuterated. In some embodiments, R A At least one of is partially or fully deuterated. In some embodiments, R B At least one of is partially or fully deuterated. In some embodiments, R E At least one of is partially or fully deuterated. In some embodiments, R F In some embodiments, at least one of R or R' is partially or fully deuterated.

[0331] In some embodiments of Formula II, at least one R A is or comprises an electron withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R A is or comprises an electron withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R A is or comprises an electron withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R A is or comprises an electron withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R Ais or comprises an electron withdrawing group from the π-EWG list as defined herein.

[0332] In some embodiments of Formula II, at least one R B is or comprises an electron withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R B is or comprises an electron withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R B is or comprises an electron withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R B is or comprises an electron withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R B is or comprises an electron withdrawing group from the π-EWG list as defined herein.

[0333] In some embodiments of Formula II, at least one R E is or comprises an electron withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R E is or comprises an electron withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R E is or comprises an electron withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R E is or comprises an electron withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R E is or comprises an electron withdrawing group from the π-EWG list as defined herein.

[0334] In some embodiments of Formula II, at least one R F is or comprises an electron withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R F is or comprises an electron withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R F is or comprises an electron withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R F is or comprises an electron withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R F is or comprises an electron withdrawing group from the π-EWG list as defined herein.

[0335] In some embodiments, Formula II comprises an electron withdrawing group from the EWG1 list as defined herein. In some embodiments, Formula II comprises an electron withdrawing group from the EWG2 list as defined herein. In some embodiments, Formula II comprises an electron withdrawing group from the EWG3 list as defined herein. In some embodiments, Formula II comprises an electron withdrawing group from the EWG4 list as defined herein. In some embodiments, Formula II comprises an electron withdrawing group from the π-EWG list as defined herein.

[0336] In some embodiments, moiety E and moiety F are both 6-membered aromatic rings.

[0337] In some embodiments, moiety F is a 5- or 6-membered heteroaromatic ring.

[0338] In some embodiments, L 4 It is O or CR'R".

[0339] In some embodiments, Z 6 is N and Z 5 It’s C.

[0340] In some embodiments, Z 6 It is C and Z 5 It's N.

[0341] In some embodiments, L 2 It is a direct key.

[0342] In some embodiments, L 2 It's NR'.

[0343] In some embodiments, K 1 , K 2 , K 3 and K 4 All are direct keys.

[0344] In some embodiments, K 1 , K 2 , K 3 and K 4 One of them is O.

[0345] In some embodiments, the compound is selected from the group consisting of compounds having the formula Pt(L A' )(Ly) is a group of compounds:

[0346]

[0347] Among them L A' Select from the group consisting of the structures shown in Listing 10 below:

[0348]

[0349]

[0350] Each R A' and R B' are independently hydrogen or selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, germanyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thiol, sulfinyl, sulfonyl, phosphino, and combinations thereof;

[0351] L 1 -L 4 each of which is independently a direct bond or selected from the group consisting of O, S, Se, NR, BR, BRR', PR, CR, C=O, C=NR, C=CRR', C=S, CRR', SO, SO2, P(O)R, SiRR', and GeRR';

[0352] The remaining variables are the same as defined previously;

[0353] Among them L y Select from the group consisting of the structures shown in Listing 11 below:

[0354]

[0355]

[0356]

[0357] where R X and R Y are independently hydrogen or selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, germanyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thiol, sulfinyl, sulfonyl, phosphino, and combinations thereof;

[0358] The remaining variables are the same as defined previously;

[0359] In some embodiments, the compound is selected from the group consisting of compounds having the formula Pt(L A' )(Ly) is a group of compounds:

[0360]

[0361] Among them L A' Selected from the group consisting of:

[0362] Ligand L A' Selected from L A' w-(Rm)(Rn)(Ro)(Lp)(Eq), wherein w is an integer from 1 to 14; each of Rm, Rn and Ro is independently selected from R1 to R468, Lp is independently selected from L1 to L6, Eq is independently selected from E1 to E12, and L A' Each of these is defined in Listing 12 below:

[0363]

[0364]

[0365] Among them L y Selected from the group consisting of:

[0366] Ligand L y Selected from L y j-(Rs)(Rt)(Ru)(Rv), wherein j is an integer from 1 to 52; each of Rs, Rt, Ru and Rv is independently selected from R1 to R468, and L y Each of these is defined in Listing 13 below:

[0367]

[0368]

[0369]

[0370]

[0371]

[0372] where R1 to R468 have the following structure (Listing 14):

[0373]

[0374]

[0375]

[0376]

[0377]

[0378]

[0379]

[0380]

[0381]

[0382]

[0383]

[0384]

[0385]

[0386]

[0387]

[0388]

[0389]

[0390]

[0391]

[0392]

[0393]

[0394] Where L1 to L have the following structure:

[0395]

[0396] Where E1 to E12 have the following structure from Listing 15 below:

[0397]

[0398] In some embodiments, the compound is selected from the group consisting of the structures in Listing 16 below:

[0399]

[0400]

[0401] In some embodiments, at least one of moiety A, moiety B, moiety E, and moiety F can each be independently selected from the group consisting of benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole, triazole, naphthalene, quinoline, isoquinoline, quinazoline, benzofuran, aza-benzofuran, benzoxazole, aza-benzoxazole, benzothiophene, Aza-benzothiophene, benzothiazole, aza-benzothiazole, benzoselenophene, aza-benzoselenophene, indene, aza-indene, indole, aza-indole, benzimidazole, aza-benzimidazole, carbazole, aza-carbazole, dibenzofuran, aza-dibenzofuran, dibenzothiophene, aza-dibenzothiophene, quinoxaline, phthalazine, phenanthrene, aza-phenanthrene, anthracene, aza-anthracene, phenanthridine, fluorene and aza-fluorene.

[0402] In some embodiments, at least one of portion A, portion B, portion E, and portion F may independently be a polycyclic fused ring structure. In some embodiments, at least one of portion A, portion B, portion E, and portion F may 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 may coordinate with the metal. In some embodiments, the polycyclic fused ring structure has two 6-membered rings. In some embodiments, at least one of portion A, portion B, portion E, and portion F may independently be selected from the group consisting of benzofuran, benzothiophene, benzoselenophene, naphthalene, and aza-variants thereof.

[0403] In some embodiments, at least one of moiety A, moiety B, moiety E, and moiety F can independently be a polycyclic fused ring structure comprising at least three fused rings. In some embodiments, the polycyclic fused ring structure has two 6-membered rings and one 5-membered ring. In some such embodiments, the 5-membered ring is fused to the ring coordinated to the metal M, and the second 6-membered ring is fused to the 5-membered ring. In some embodiments, at least one of moiety A, moiety B, moiety E, and moiety F can independently be selected from the group consisting of dibenzofuran, dibenzothiophene, dibenzoselenophene, and aza-variants thereof. In some such embodiments, at least one of moiety A, moiety B, moiety E, and moiety F can independently be further substituted at the ortho or meta position relative to the O, S, or Se atom with a substituent selected from the group consisting of deuterium, fluorine, nitrile, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof. In some such embodiments, the aza-variant contains exactly one N atom at the 6-position (ortho to the O, S, or Se) and a substituent at the 7-position (meta to the O, S, or Se).

[0404] In some embodiments, at least one of moiety A, moiety B, moiety E, and moiety F 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.

[0405] In some embodiments, at least one of part A, part B, part E, and part F 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 a 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.

[0406] In some embodiments, at least one of portion A, portion B, portion E, and portion F may independently be an aza form of the polycyclic fused ring described above. In some such embodiments, at least one of portion A, portion B, portion E, and portion F may independently contain exactly one aza-N atom. In some such embodiments, at least one of portion A, portion B, portion E, and portion F may contain exactly two aza-N atoms, which may be in one ring or in two different rings. In some such embodiments, the ring with the aza-N atom is separated from the metal M atom by at least two other rings. In some such embodiments, the ring with the aza-N atom is separated from the metal M atom by at least three other rings. In some such embodiments, each of the ortho positions of the aza-N atom is substituted.

[0407] In some embodiments, the first ligand L having Formula I described herein is AThe compound can be at least 30% deuterated, at least 40% deuterated, at least 50% deuterated, at least 60% deuterated, at least 70% deuterated, at least 80% deuterated, at least 90% deuterated, at least 95% deuterated, at least 99% deuterated or 100% deuterated. As used herein, deuteration percentage has its ordinary meaning and includes the percentage of all possible hydrogen atoms (such as hydrogen or deuterium positions) occupied by deuterium atoms in the compound. In some embodiments, the carbon atoms constituting the ring coordinated to the metal M are fully or partially deuterated. In some embodiments, the carbon atoms included by the polycyclic system coordinated to the metal M are fully or partially deuterated. In some embodiments, the substituents connected to the monocyclic or fused polycyclic system coordinated to the metal M are fully or partially deuterated.

[0408] In some embodiments, the emission of the compound of Formula I at room temperature has a full width at half maximum (FWHM) equal to or less than 50, 45, 40, 35, 30, 25, 20, 15, 10, or 5 nm. A narrower FWHM means better color purity for OLED display applications.

[0409] In the case of a compound having the formula M(L A ) p (L B ) q (L C ) r In some embodiments of the heteroleptic compound, the ligand L A Having a first substituent R I , wherein the first substituent R I The first atom aI in the ligand L A The farthest from the metal M among all atoms in the ligand L B (if present) has a second substituent R II , wherein the second substituent R II The first atom a-II in the ligand L B The farthest from the metal M among all atoms in C (if present) has a third substituent R III , wherein the third substituent R III The first atom a-III in the ligand L C It is the farthest from the metal M among all the atoms in the molecule.

[0410] In such heteroleptic compounds, the vector V can be defined D1 、V D2 and V D3 , which is defined as follows. V D1 represents the direction from the metal M to the first atom aI, and the vector V D1 The value of D 1 Represents the metal M and the first substituent RI The straight-line distance between the first atoms aI in V D2 represents the direction from the metal M to the first atom a-II, and the vector V D2 The value of D 2 Represents the metal M and the second substituent R II The straight-line distance between the first atoms a-II in V D3 represents the direction from the metal M to the first atom a-III, and the vector V D3 The value of D 3 Represents the metal M and the third substituent R III The straight-line distance between the first atoms a-III in .

[0411] In such heteroleptic compounds, a sphere with radius r is defined, the center of which is the metal M and the radius r is the radius that allows the sphere to enclose the substituents R in the compound that are not I 、R II and R III The smallest radius of all atoms that are part of 1 、D 2 and D 3 At least one of them is larger than the radius r by at least In some embodiments, D 1 、D 2 and D 3 At least one of the following is greater than the radius r by at least 2.9, 3.0, 4.3, 4.4, 5.2, 5.9, 7.3, 8.8, 10.3, 13.1, 17.6 or In some embodiments, D 1 、D 2 and D 3 At least two of the radius r are at least 1.5, 2.9, 3.0, 4.3, 4.4, 5.2, 5.9, 7.3, 8.8, 10.3, 13.1, 17.6 or more

[0412] In some embodiments of such heteroleptic compounds, the compound has a transition dipole moment axis, and the transition dipole moment axis is aligned with the vector V D1 、V D2 and V D3 The angle between the transition dipole moment axis and the vector V is determined. D1 、V D2 and V D3 In some embodiments, the transition dipole moment axis and the vector V D1 、V D2 and V D3At least one angle between the transition dipole moment axis and the vector V is less than 30°, 20°, 15°, or 10°. D1 、V D2 and V D3 In some embodiments, the transition dipole moment axis and the vector V D1 、V D2 and V D3 At least two of the angles therebetween are smaller than 15° or 10°.

[0413] In some embodiments, the transition dipole moment axis is aligned with the vector V D1 、V D2 and V D3 All three angles between them are less than 20°. In some embodiments, the transition dipole moment axis is aligned with the vector V D1 、V D2 and V D3 All three angles between them are less than 15° or 10°.

[0414] In some embodiments of such heteroleptic compounds, the compound has a vertical dipole ratio (VDR) of 0.33 or less. In some embodiments of such heteroleptic compounds, the compound has a VDR of 0.30, 0.25, 0.20, or 0.15 or less.

[0415] A person skilled in the art will readily understand the meaning of the terms transition dipole moment axis of a compound and vertical dipole ratio of a compound. However, the meaning of these terms can be found in U.S. Patent No. 10,672,997, the disclosure of which is incorporated herein by reference in its entirety. In U.S. Patent No. 10,672,997, the horizontal dipole ratio (HDR) of a compound is discussed, not the VDR. However, a person skilled in the art will readily understand that VDR = 1 - HDR.

[0416] In some embodiments, the compound can be an emitting dopant. In some embodiments, the compound can produce emission via phosphorescence, fluorescence, thermally activated delayed fluorescence, triplet-triplet elimination, or a combination of these methods. In some embodiments, the emitting dopant can be a racemic mixture, or can be enriched in one enantiomer. In some embodiments, the compounds of the present invention can have different stereoisomers, such as fac and mer. The current compound relates to a mixture of individual isomers and various isomers of any mixing ratio. In some embodiments, the compound can be homogeneous (each ligand is the same). In some embodiments, the compound can be mixed (at least one ligand is different from the others). In some embodiments, when there is more than one ligand coordinated to the metal, the ligands can all be the same. In some other embodiments, at least one ligand is different from the other ligands. In some embodiments, each ligand can be different from all other ligands. This is also true in the following embodiments, where the ligand coordinated to the metal can be connected to other ligands coordinated to the metal to form a tridentate, quadridentate, pentadentate, or hexadentate ligand. Thus, where coordinating ligands are linked together, in some embodiments all of the ligands may be identical, and in some other embodiments at least one of the linked ligands may be different from the other ligands.

[0417] In another aspect of the present disclosure, a formulation comprising the novel compounds disclosed herein is described. The formulation may include one or more components disclosed herein selected from the group consisting of a solvent, an emitter, a host, a hole injection material, a hole transport material, an electron blocking material, a hole blocking material, and an electron transport material.

[0418] The present disclosure encompasses any chemical structure comprising a novel compound of the present disclosure or a monovalent or multivalent variant thereof. In other words, the compounds of the present invention or their monovalent or multivalent variants can be part of a larger chemical structure. Such chemical structures can be selected from the group consisting of: monomers, polymers, macromolecules, and supramolecules (also referred to as supermolecules). As used herein, a "monovalent variant of a compound" refers to a portion identical to the compound, but one of the hydrogen atoms has been removed and replaced with a bond to the rest of the chemical structure. As used herein, a "multivalent variant of a compound" refers to a portion identical to the compound, but more than one hydrogen atom has been removed and replaced with one or more bonds to the rest of the chemical structure. In the case of a supramolecule, the compounds of the present invention can also be incorporated into supramolecular complexes without covalent bonds. As used in this context, the description that structure A includes part B means that structure A includes the structure of part B, and the structure of part B does not include H or D atoms that can be connected to part B. This is because at least one H or D on a given part structure must be replaced with a substituent so 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 part B structure can be further substituted.

[0419] In some embodiments, each of moiety A, moiety B, moiety E, and moiety F can be independently selected from the group consisting of benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole, triazole, naphthalene, quinoline, isoquinoline, quinazoline, benzofuran, aza-benzofuran, benzoxazole, aza-benzoxazole, benzothiophene, nitrogen hetero-benzothiophene, benzothiazole, aza-benzothiazole, benzoselenophene, aza-benzoselenophene, indene, aza-indene, indole, aza-indole, benzimidazole, aza-benzimidazole, carbazole, aza-carbazole, dibenzofuran, aza-dibenzofuran, dibenzothiophene, aza-dibenzothiophene, quinoxaline, phthalazine, phenanthrene, aza-phenanthrene, anthracene, aza-anthracene, phenanthridine, fluorene and aza-fluorene.

[0420] In some embodiments, each of portion A, portion B, portion E, and portion F can independently be a polycyclic fused ring structure. In some embodiments, each of portion A, portion B, portion E, and portion F can independently be a polycyclic fused ring structure comprising at least two fused rings. In some embodiments, the polycyclic fused ring structure has one 6-membered ring and one 5-membered ring. In some such embodiments, the 5-membered ring or the 6-membered ring can coordinate with the metal. In some embodiments, the polycyclic fused ring structure has two 6-membered rings. In some embodiments, each of portion A, portion B, portion E, and portion F can independently be selected from the group consisting of benzofuran, benzothiophene, benzoselenophene, naphthalene, and aza-variants thereof.

[0421] In some embodiments, each of moiety A, moiety B, moiety E, and moiety F can independently be a polycyclic fused ring structure comprising at least three fused rings. In some embodiments, the polycyclic fused ring structure has two 6-membered rings and one 5-membered ring. In some such embodiments, the 5-membered ring is fused to the ring coordinated to the metal M, and the second 6-membered ring is fused to the 5-membered ring. In some embodiments, each of moiety A, moiety B, moiety E, and moiety F can independently be selected from the group consisting of dibenzofuran, dibenzothiophene, dibenzoselenophene, and aza-variants thereof. In some such embodiments, each of moiety A, moiety B, moiety E, and moiety F can independently be further substituted at the ortho or meta position relative to the O, S, or Se atom with a substituent selected from the group consisting of deuterium, fluorine, nitrile, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof. In some such embodiments, the aza-variant contains exactly one N atom at the 6-position (ortho to the O, S, or Se) and a substituent at the 7-position (meta to the O, S, or Se).

[0422] In some embodiments, each of moiety A, moiety B, moiety E, and moiety F 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.

[0423] In some embodiments, each of part A, part B, part E and part F 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 with a 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.

[0424] In some embodiments, each of portion A, portion B, portion E, and portion F can independently be an aza version of the polycyclic fused ring described above. In some such embodiments, each of portion A, portion B, portion E, and portion F can independently contain exactly one aza-N atom. In some such embodiments, at least one of portion A, portion B, portion E, and portion F contains exactly two aza-N atoms, which can be in one ring or in two different rings. In some such embodiments, the ring with the aza-N atom is separated from the metal M atom by at least two other rings. In some such embodiments, the ring with the aza-N atom is separated from the metal M atom by at least three other rings. In some such embodiments, each of the ortho positions of the aza-N atom is substituted.

[0425] In some embodiments of Formula I, at least one R A 、R B 、R E or R F is partially or fully deuterated. In some embodiments, at least one R A is partially or fully deuterated. In some embodiments, at least one R B is partially or fully deuterated. In some embodiments, at least one R E is partially or fully deuterated. In some embodiments, at least one R F is partially or fully deuterated. In some embodiments, R α or R β At least one of R, R', R α 、R β 、R A 、R B 、R C 、R D 、R E 、R F or R G At least one of is a substituent selected from the group consisting of general substituents defined herein.

[0426] C. OLEDs and Devices of the Present Disclosure

[0427] In another aspect, the present disclosure also provides an OLED device comprising a first organic layer containing a compound as disclosed in the above compound section of the present disclosure.

[0428] 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 described herein.

[0429] 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 may be an emissive layer and the compound as described herein may be an emissive dopant or a non-emissive dopant.

[0430] In some embodiments, the organic layer may further comprise a host, wherein the host comprises at least one chemical group selected from the group consisting of triphenylene, carbazole, indolecarbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, 5λ 2 -benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, 5,9-dioxa-13b-borazinonaphtho[3,2,1-de]anthracene, azaborane, oxaborabene, dihydroacridine, xanthene, dihydrobenzoazasiline, dibenzooxasiline, phenoxazine, phenoxathiol, phenothiazine, dihydrophenazine, fluorene, naphthalene, anthracene, phenanthrol, phenanthroline, benzoquinoline, quinoline, isoquinoline, quinazoline, pyrimidine, pyrazine, pyridine, triazine, borane, silane, aza-triphenylene, aza-carbazole, aza-indolocarbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, aza-5λ 2 -benzo[d]benzo[4,5]imidazo[3,2-a]imidazole and aza-(5,9-dioxa-13b-borazinonaphtho[3,2,1-de]anthracene).

[0431] In some embodiments, the subject may be selected from the group consisting of the following structures of Listing 17 (also referred to herein as Subject Group 1):

[0432]

[0433]

[0434]

[0435]

[0436]

[0437]

[0438]

[0439]

[0440]

[0441] in:

[0442] Each of J1 to J6 is independently C or N;

[0443] L' is a direct bond or an organic linking group;

[0444] Each Y AA 、Y BB 、Y CC and Y DD independently selected from the group consisting of: absence of bond, direct bond, O, S, Se, CRR', SiRR', GeRR', NR, BR, BRR';

[0445] R A' 、R B' 、R C' 、R D' 、R E' 、R F' and R G' Each of independently represents monosubstitution, up to maximum substitution, or no substitution;

[0446] Each R, R', R A' 、R B' 、R C' 、R D' 、R E' 、R F' and R G' is independently hydrogen or a substituent selected from the group consisting of general substituents as defined herein; any two substituents may be joined or fused to form a ring;

[0447] Also, where possible, each unsubstituted aromatic carbon atom is optionally replaced with N to form an aza-substituted ring.

[0448] In some embodiments, at least one of J1 to J3 is N. In some embodiments, at least two of J1 to J3 are N. In some embodiments, all three of J1 to J3 are N. In some embodiments, each Y CC and Y DD R and R are independently O, S, or SiRR', or more preferably O or S. In some embodiments, at least one unsubstituted aromatic carbon atom is replaced with N to form an nitrogen heterocycle.

[0449] In some embodiments, the host is selected from the group consisting of EG1-MG1-EG1 to EG53-MG27-EG53 of the formula EGa-MGb-EGc, or EG1-EG1 to EG53-EG53 of the formula EGa-EGc when 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 EG1 to EG53 are shown below:

[0450]

[0451]

[0452] The structures of MG1 to MG27 are shown below:

[0453]

[0454] In the MGb structures shown above, the two bonding positions in the asymmetric structures MG10, MG11, MG12, MG13, MG14, MG17, MG24, and MG25 are labeled with numbers for identification purposes.

[0455] In some embodiments, the subject can be any of its aza-substituted variants, its fully or partially deuterated variants, and combinations thereof. In some embodiments, the subject has the formula EGa-MGb-Egc and is selected from the group consisting of h1 to h112 as defined in the following Listing of Subject Group 2, wherein each of MGb, EGa, and EGc is defined as follows:

[0456]

[0457]

[0458] In the table above, EGa and EGc structures bonded to one of the asymmetric structures MG10, MG11, MG12, MG13, MG14, MG17, MG24, and MG25 are annotated with a numerical prefix identifying their bonding position in the MGb structure.

[0459] In some embodiments, the organic layer may further comprise a host, wherein the host comprises a metal complex.

[0460] In some embodiments, the emissive layer may include two hosts: a first host and a second host. In some embodiments, the first host is a hole-transporting host, and the second host is an electron-transporting host. In some embodiments, the first host is a hole-transporting host, and the second host is a bipolar host. In some embodiments, the first host is an electron-transporting host, and the second host is a bipolar host. In some embodiments, the first host and the second host may form an exciplex. In some embodiments, the emissive layer may include a third host. In some embodiments, the third host is selected from the group consisting of an insulating host (wide bandgap host), a hole-transporting host, and an electron-transporting host. In some embodiments, the third host forms an exciplex with one of the first and second hosts, or with both the first and second hosts. In some embodiments, the emissive layer may include a fourth host. In some embodiments, the fourth host is selected from the group consisting of an insulating host (wide bandgap host), a hole-transporting host, and an electron-transporting host. In some embodiments, the fourth host forms an exciplex with one of the first, second, and third hosts, with both of the first, second, and third hosts, or with each of the first, second, and third hosts. In some embodiments, the LUMO of the electron transport host is less than -2.4 eV, less than -2.5 eV, less than -2.6 eV or less than -2.7 eV. In some embodiments, the HOMO of the hole transport host is greater than -5.6 eV, greater than -5.5 eV, greater than -5.4 eV or greater than -5.35 eV. HOMO and LUMO values ​​can be determined using solution electrochemistry. Solution cyclic voltammetry and differential pulse voltammetry can be performed using a CH instrument model 6201B potentiostat using anhydrous dimethylformamide (DMF) solvent and tetrabutylammonium hexafluorophosphate as a supporting electrolyte. Glassy carbon, platinum wire, and silver wire are used as working electrode, counter electrode, and reference electrode, respectively. By measuring the peak potential difference by differential pulse voltammetry, the electrochemical potential can be referenced to the internal ferrocene-ferrocene salt redox pair (Fc / Fc+).According to the literature ((a) Fink, R.; Heischkel, Y.; Thelakkat, M.; Schmidt, H.-W., Chem. Mater. 1998, 10, 3620-3625; (b) Pommerehne, J.; Vestweber, H.; Geiss, W. The energies of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) were determined by comparing the cation and anion redox potentials with those of a ferrocene reference (4.8 EV relative to vacuum).

[0461] In some embodiments, the compounds described herein may be sensitizers or components of sensitizers; wherein the device may 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 may be a fluorescent material. In some embodiments, the compounds described herein may be used as phosphorescent sensitizers in OLEDs, 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, the compounds described herein may be used as a component of an exciplex used as a sensitizer. As a phosphorescent sensitizer, the compound must be able to transfer energy to the acceptor and the acceptor will emit energy or further transfer energy to the final emitter. The acceptor concentration may range from 0.001% to 99.9%. The acceptor may 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 fluorescent (TADF) material. In some embodiments, the acceptor is a non-delayed fluorescent material. In some embodiments, emission may be generated by any or all of the sensitizer, the acceptor, and the final emitter. In some embodiments, the emission of the acceptor at room temperature has a full width at half maximum (FWHM) equal to or less than 50, 45, 40, 35, 30, 25, 20, 15, 10, or 5 nm. Narrower FWHM means better color purity for OLED display applications.

[0462] As used herein, phosphorescence generally refers to the emission of photons when the electron spin quantum number changes, that is, the initial and final states of the emission have different electron spin quantum numbers, such as from the T1 to the S0 state. Most of the Ir and Pt complexes currently used in OLEDs are phosphorescent emitters. In some embodiments, if the exciplex formation involves a triplet emitter, then such exciplexes can also emit phosphorescence. On the other hand, a fluorescent emitter generally refers to the emission of photons when the electron spin quantum number does not change, such as from the S1 to the S0 state, or from the D1 to the D0 state. A fluorescent emitter can be a delayed fluorescent emitter or a non-delayed fluorescent emitter. Depending on the spin state, a fluorescent emitter can be a singlet emitter or a doublet emitter or other multiplet emitter. It is believed that the internal quantum efficiency (IQE) of a fluorescent OLED can exceed the 25% spin statistical limit through delayed fluorescence. There are two types of delayed fluorescence, namely P-type and E-type delayed fluorescence. P-type delayed fluorescence is produced by triplet-triplet annihilation (TTA). On the other hand, E-type delayed fluorescence does not rely on the collision of two triplets, but relies on the thermal population between the triplet and singlet excited states. Thermal energy can activate the triplet transition back to the singlet state. This type of delayed fluorescence is also known as TADF. E-type delayed fluorescence characteristics can be found in exciplex systems or single compounds. Without being bound by theory, it is believed that TADF emission needs to have a small singlet-triplet energy gap (ΔE) of less than or equal to 400, 350, 300, 250, 200, 150, 100 or 50 meV. S-T ) compounds or excited complexes. 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 connecting an electron donor portion (such as an amino or carbazole derivative) and an electron acceptor portion (such as an N-containing six-membered aromatic ring or a cyano-substituted aromatic ring). A donor-acceptor excited complex can be formed between a hole transport compound and an electron transport compound. Examples of MR-TADF materials include highly conjugated fused ring systems. In some embodiments, MR-TADF materials contain boron, carbon, and nitrogen atoms. Such materials may also contain other atoms, such as oxygen. In some embodiments, the reverse intersystem crossing time from T1 to S1 of delayed fluorescence emission at 293K is less than or equal to 10 microseconds. In some embodiments, such time may be greater than 10 microseconds and less than 100 microseconds.

[0463] In some embodiments, the OLED can include additional compounds selected from the group consisting of: non-delayed fluorescent materials, delayed fluorescent materials, phosphorescent materials, and combinations thereof.

[0464] In some embodiments, the compounds of the invention described herein are phosphorescent materials.

[0465] In some embodiments, the phosphorescent material is an emitter that emits light within the OLED. In some embodiments, the phosphorescent material does not emit light within the OLED. In some embodiments, the phosphorescent material transfers energy from its excited state to another material within the OLED. In some embodiments, the phosphorescent material participates in charge transport within the OLED. In some embodiments, the phosphorescent material is a sensitizer or a component of a sensitizer, and the OLED further comprises an acceptor. In some embodiments, the phosphorescent material forms an exciplex with another material within the OLED (e.g., a host material, an emitter material).

[0466] 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 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.

[0467] 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-metallic 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-carbon olefin bond. In some embodiments, the non-delayed fluorescent material or the 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-borazinnaphtho[3,2,1-de]anthracene, 5λ 2 ,9λ 2 -diaza-13b-borazinnaphtho[2,3,4-de]anthracene, 5-oxa-9λ 2-aza-13b-borazinahxa[3,2,1-de]anthracene, azaborane, oxaborabine, dihydroacridine, xanthracene, dihydrobenzoazasilane, dibenzooxasilane, phenoxazine, phenoxathiol, phenothiazine, dihydrophenazine, fluorene, naphthalene, anthracene, phenanthrol, phenanthroline, benzoquinoline, quinoline, isoquinoline, quinazoline, pyrimidine, pyrazine, pyridine, triazine, borane, amino, silane, aza variants thereof, and combinations thereof. In some embodiments, the non-delayed fluorescent material or delayed fluorescent material comprises tri(aryl / heteroaryl)borane, wherein one or more pairs of substituents from aryl / heteroaryl groups are joined to form a ring. In some embodiments, the fluorescent material comprises at least one chemical group selected from the group consisting of naphthalene, anthracene, phenanthracene, phenanthracene, fluorene, pyrene, Perylene and Azulene.

[0468] In yet another aspect, the OLED of the present disclosure may further comprise an emissive region comprising a compound or formulation of compounds as disclosed in the above compound section of the present disclosure. In some embodiments, the emissive region may comprise a compound or formulation of compounds as described herein. In some embodiments, the emissive region is comprised of one or more organic layers, wherein at least one of the one or more organic layers has a minimum thickness selected from the group consisting of: 350, 400, 450, 500, 550, 600, 650, and In some embodiments, at least one of the one or more organic layers is formed from an emissive system having a figure of merit (FOM) equal to or greater than a value selected from the group consisting of: 2.50, 2.55, 2.60, 2.65, 2.70, 2.75, 2.80, 2.85, 2.90, 2.95, 3.00, 5.00, 10.0, 15.0, and 20.0. The definition of FOM can be found 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 compounds as disclosed in Sections A and D of this disclosure.

[0469] In some embodiments, the OLEDs or emission regions comprising the compounds of the present invention disclosed herein can be incorporated into a full-color pixel arrangement of a device. The full-color pixel arrangement of such a device comprises at least one pixel, wherein the at least one pixel comprises a first subpixel and a second subpixel. The first subpixel comprises a first OLED comprising a first emission region. The second subpixel comprises a second OLED comprising a second emission region. In some embodiments, the first and / or second OLED, the first and / or second emission regions may be the same or different and each may independently have various device features and various embodiments of the compounds of the present invention included therein, as well as various combinations and sub-combinations of various device features and various embodiments of the compounds of the present invention included therein, as disclosed herein.

[0470] In some embodiments, the first emission region is configured to emit light having a peak wavelength λ max1 The second emission region is configured to emit light having a peak wavelength λ max2 In some embodiments, the peak wavelength λ max1 and λ max2 The difference between the two is at least 4 nm but within the same color. For example, light blue and dark blue light as described above. In some embodiments, the first emission region is configured to emit light having a peak wavelength λ in one region of the visible spectrum of 400-500 nm, 500-600 nm, 600-700 nm. max1 and the second emission region is configured to emit light having a peak wavelength λ in one of the remaining regions of the visible spectrum of 400-500nm, 500-600nm, 600-700nm; max2 In some embodiments, the first emission region comprises (if more than one) a first number of emission layers deposited one above the other; and the second emission region comprises (if more than one) a second number of emission layers deposited one above the other; and the first number is different from the second number. In some embodiments, both the first emission region and the second emission region comprise phosphorescent materials, which may be the same or different. In some embodiments, the first emission region comprises a phosphorescent material and the second emission region comprises a fluorescent material. In some embodiments, both the first emission region and the second emission region comprise fluorescent materials, which may be the same or different.

[0471] In some embodiments, the OLED or at least one pixel of the emissive region includes a total of N subpixels; wherein the N subpixels include a first subpixel and a second subpixel; wherein each of the N subpixels includes 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 subpixel of the at least one pixel includes an emissive region that is identical to the first emissive region. In some embodiments, a full-color pixel arrangement can have a plurality of pixels including a first pixel region and a second pixel region; wherein at least one display feature in the first pixel region is different from a corresponding display feature in the second pixel region, and wherein the at least one display feature is selected from the group consisting of: resolution, cavity mode, color, outcoupling, and color filter.

[0472] 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 emission region disposed above the first electrode, a first CGL disposed above the first emission region, a second emission region disposed above the first CGL, and a second electrode disposed above the second emission region. In some embodiments, the first emission region and / or the second emission region may have various device features as described above for pixelated devices. In some embodiments, the stacked OLED is configured to emit white. In some embodiments, one or more of the emission regions in the pixelated OLED or stacked OLED comprises a sensitizer and an acceptor having various sensitizing device features and various embodiments of the compounds of the present invention disclosed herein. For example, the first emission region is included in the sensitizing device, while the second emission region is not included in the sensitizing device; in some cases, both the first emission region and the second emission region are included in the sensitizing device.

[0473] In some embodiments, the OLED can emit at least 1%, 5%, 10%, 30%, 50%, 70%, 80%, 90%, 95%, 99% or 100% of the light from the plasmon mode. In some embodiments, at least one of the anode, cathode or a new layer disposed above the organic emissive layer serves as an enhancement layer. The enhancement layer comprises a plasmon material exhibiting surface plasmon resonance, the plasmon material non-radiatively couples to the emitter material and transfers excited state energy from the emitter material to a non-radiative mode 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, wherein 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 the position where the total non-radiative decay rate constant is equal to the total radiative decay rate constant. Another threshold distance is the distance 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 is equal to the photoluminescence yield of the emissive material in the absence of the enhancement layer.

[0474] In some embodiments, the OLED further comprises an outcoupling layer. In some embodiments, the outcoupling layer is disposed above the enhancement layer on the side opposite the organic emissive layer. The outcoupling layer scatters energy from the surface plasmon polaritons. In some embodiments, this energy is scattered into free space as photons. In other embodiments, energy is scattered from the surface plasmon 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 intermediate layers may be disposed between the enhancement layer and the outcoupling layer. Examples of intermediate layers may be dielectric materials, including organic, inorganic, perovskite, oxides, and may include stacks and / or mixtures of these materials.

[0475] The enhancement layer modifies 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, variation in emission intensity with angle, altered emitter material stability, altered OLED efficiency, and reduced roll-off efficiency of the OLED device. Placing the enhancement layer on the cathode side, the anode side, or both, or placing the enhancement layer itself as a CGL, produces an OLED device that utilizes any of the aforementioned effects. In addition to the specific functional layers described herein and illustrated in the various OLED examples shown in the figures, OLEDs according to the present disclosure may also include any other functional layers commonly found in OLEDs.

[0476] In some embodiments, the enhancement layer may comprise a plasmonic material, an optically active metamaterial, or a hyperbolic metamaterial. In some embodiments, the plasmonic material comprises at least one metal. In such embodiments, the metal may 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 thereof, and stacks of such materials. In some embodiments, the enhancement layer is configured as a planar layer. In other embodiments, the enhancement layer has wavelength-sized features arranged periodically, quasi-periodically, or randomly, or has sub-wavelength-sized features arranged periodically, quasi-periodically, or randomly.

[0477] In some embodiments, the outcoupling layer has wavelength-sized or subwavelength-sized features that are periodically, quasi-periodically, or randomly arranged. 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, adjusting the thickness of the material, changing the refractive index of the material, adding an additional layer disposed above the plurality of nanoparticles, changing the thickness of the reinforcement layer, or changing the material of the reinforcement layer. The plurality of nanoparticles of the device can be formed from at least one of the following: a metal, a dielectric material, a semiconductor material, a metal alloy, a mixture of dielectric materials, a stack or layer of one or more materials, and / or a core of one type of material coated with a shell of another type of material. In some embodiments, the outcoupling layer is composed of at least metal nanoparticles, wherein the metal is selected from the group consisting of Ag, Al, Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ru, Pd, In, Bi, and Ca, alloys or mixtures of these materials, and stacks of these materials. In some embodiments, the outcoupling layer is formed by photolithography.

[0478] In some embodiments of plasmonic devices, the emitter and / or host compound used in the emissive 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.

[0479] 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 may comprise a compound or a formulation of compounds as disclosed in the above compound section of the present disclosure.

[0480] In some embodiments, a 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 a compound as described herein.

[0481] In general, an OLED comprises at least one organic layer disposed between and electrically connected to an anode and a cathode. When an electric current is applied, the anode injects holes and the cathode injects electrons into the organic layer. The injected holes and electrons each migrate toward the oppositely charged electrode. When electrons and holes are localized on the same molecule, "excitons" are formed, which are localized electron-hole pairs with excited energy states. When the excitons relax through a photoemission mechanism, light is emitted. In some cases, excitons can be localized as excimers or excited complexes. Non-radiative mechanisms (such as thermal relaxation) may also occur, but are generally considered undesirable.

[0482] Figure 1 An organic light-emitting device 100 is shown. The figures are not necessarily drawn to scale. Device 100 may include a substrate 110, an anode 115, a hole injection layer (HIL) 120, a hole transport layer (HTL) 125, an electron blocking layer (EBL) 130, an emissive layer (EML) 135, a hole blocking layer (HBL) 140, an electron transport layer (ETL) 145, an electron injection layer (EIL) 150, a protective layer 155, a cathode 160, and a blocking layer 170. Cathode 160 is a composite cathode having a first conductive layer 162 and a second conductive layer 164. Device 100 can be manufactured by depositing the layers in sequence. The properties and functions of these various layers and example materials are described in more detail in US Pat. No. 7,279,704, columns 6-10, which is incorporated by reference.

[0483] More examples of each of these layers are available. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. Patent No. 5,844,363, which is incorporated by reference in its entirety. An example of a p-doped hole transport layer is m-MTDATA doped with F4-TCNQ at a molar ratio of 50:1, as disclosed in U.S. Patent Application Publication No. 2003 / 0230980, which is incorporated by reference in its entirety. Examples of luminescent and host materials are disclosed in U.S. Patent No. 6,303,238 to Thompson et al., which is incorporated by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li at a molar ratio of 1:1, as disclosed in U.S. Patent Application Publication No. 2003 / 0230980, which is incorporated by reference in its entirety. U.S. Patent Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entireties, disclose examples of cathodes comprising a composite cathode having a thin layer of a metal (e.g., Mg:Ag) with an overlying 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, which are incorporated by reference in their entireties. Examples of injection layers are provided in U.S. Patent Application Publication No. 2004 / 0174116, which is incorporated by reference in its entirety. A description of protective layers can be found in U.S. Patent Application Publication No. 2004 / 0174116, which is incorporated by reference in its entirety.

[0484] 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 in sequence. Because the most common OLED configuration has the cathode positioned above the anode, and device 200 has cathode 215 positioned below anode 230, device 200 can be referred to as an "inverted" OLED. Materials similar to those described for device 100 can be used in the corresponding layers of device 200. Figure 2 An example is provided of how some layers may be omitted from the structure of device 100 .

[0485] Figure 1 and 2The simple layered structures illustrated in the are provided by way of non-limiting examples, and it will be appreciated that embodiments of the present disclosure may be used in conjunction with various other structures. The specific materials and structures described are exemplary in nature, and other materials and structures may be used. Functional OLEDs may be obtained by combining the various layers described in different ways, or layers may be omitted entirely based on design, performance, and cost factors. Other layers not specifically described may also be included. Materials other than those specifically described may be used. Although many of the examples provided herein describe the various layers as comprising a single material, it will be appreciated that combinations of materials may be used, such as mixtures of hosts and dopants, or more generally, mixtures. In addition, the layers may have various sub-layers. The names given to the various layers herein are not intended to be strictly limiting. For example, in device 200, hole transport layer 225 transports holes and injects holes into emissive layer 220, and may be described as a hole transport layer or a hole injection layer. In one embodiment, the OLED may be described as having an "organic layer" disposed between the cathode and the anode. This organic layer may comprise a single layer, or may further comprise, for example, a layer comprising a plurality of layers. Figure 1 and 2 Multiple layers of said different organic materials.

[0486] Structures and materials not specifically described may also be used, such as OLEDs comprising polymeric materials (PLEDs), such as disclosed in U.S. Pat. No. 5,247,190 to Friend et al., which is incorporated by reference in its entirety. By way of another example, an OLED having a single organic layer may be used. OLEDs may be stacked, such as described in U.S. Pat. No. 5,707,745 to Forrest et al., which is incorporated by reference in its entirety. OLED structures may deviate from Figure 1 and 2 For example, the substrate may include angled reflective surfaces to improve out-coupling, such as a mesa structure as described in U.S. Pat. No. 6,091,195 to Forrest et al., and / or a pit structure as described in U.S. Pat. No. 5,834,893 to Bulovic et al., which are incorporated by reference in their entirety.

[0487] Unless otherwise specified, any of the layers of the various embodiments may be deposited by any suitable method. For organic layers, preferred methods include thermal evaporation, inkjet (as described in U.S. Patents Nos. 6,013,982 and 6,087,196, incorporated by reference in their entirety), organic vapor phase deposition (OVPD) (as described in U.S. Patent No. 6,337,102 to Forrest et al., incorporated by reference in its entirety), and deposition by organic vapor jet printing (OVJP, also known as organic vapor jet deposition (OVJD)) (as described in U.S. Patent No. 7,431,968, incorporated by reference in its entirety). Other suitable deposition methods include spin coating and other solution-based processes. Solution-based processes are preferably carried out in nitrogen or an inert atmosphere. For other layers, preferred methods include thermal evaporation, sputtering, chemical vapor deposition, atomic layer deposition, and electron beam deposition. Preferred patterning methods include deposition through a mask, photolithography, and cold welding (as described in U.S. Patents Nos. 6,294,398 and 6,468,819, which are incorporated by reference in their entirety) and patterning associated with some of the deposition methods such as inkjet and organic vapor jet printing (OVJP). Other methods may also be used. The material to be deposited may be modified to make it compatible with the specific deposition method. For example, branched or unbranched substituents such as alkyl and aryl groups, preferably containing at least 3 carbons, may be used in small molecules to enhance their ability to withstand solution processing. Substituents with 20 or more carbons may be used, and 3 to 20 carbons are a preferred range. Materials with asymmetric structures may have better solution processability than materials with symmetrical structures because asymmetric materials may have a lower tendency to recrystallize. Dendrimer substituents may be used to enhance the ability of small molecules to withstand solution processing.

[0488] The device manufactured according to the embodiments of the present disclosure may further optionally include a barrier layer. One purpose of the barrier layer is to protect the electrodes and organic layers from damage by exposure to harmful substances in the environment including moisture, vapor and / or gas. The barrier layer can be deposited on the substrate, above the electrode, deposited below the substrate, electrode or deposited next to the substrate, electrode, or deposited above any other part of the device (including the edge). The barrier layer can comprise a single layer or multiple layers. The barrier layer can be formed by various known chemical vapor deposition techniques and can include compositions having a single phase and compositions having multiple phases. Any suitable material or combination of materials can be used for the barrier layer. The barrier layer can be combined with an inorganic compound or an organic compound or both. Preferred barrier layers comprise multiple alternate layers of: polymeric and non-polymeric materials; organic and inorganic materials; or a mixture of polymeric and non-polymeric materials, an example of which is described in U.S. Patent No. 7,968,146, PCT Patent Application Nos. PCT / US2007 / 023098, and PCT / US2009 / 042829, which are incorporated herein by reference in their entirety.

[0489] The devices manufactured according to the embodiments of the present disclosure can be incorporated into a wide variety of electronic component modules (or units), which can be incorporated into a wide variety of electronic products or intermediate components. Examples of the electronic products or intermediate components 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 component module can optionally include driving electronic devices and / or power supplies. The devices manufactured according to the embodiments of the present disclosure can be incorporated into a wide variety of consumer products, which have one or more electronic component modules (or units) incorporated therein. A consumer product comprising an OLED is disclosed, wherein the OLED includes a compound of the present disclosure in an organic layer in the OLED. The consumer product should include any kind of product containing one or more of one or more light sources and / or some type of visual display. Some examples of such consumer products include flat panel displays, curved displays, computer monitors, medical monitors, televisions, billboards, lights for interior or exterior lighting and / or signaling, heads-up displays, fully or partially transparent displays, flexible displays, rollable displays, foldable displays, stretchable displays, laser printers, phones, cellular phones, tablet computers, tablet phones, personal digital assistants (PDAs), wearable devices, laptop computers, digital cameras, video cameras, viewfinders, microdisplays (displays with a diagonal of less than 2 inches), 3-D displays, virtual reality or augmented reality displays, vehicles, video walls comprising multiple displays tiled together, theater or stadium screens, light therapy devices, and signage. Various control mechanisms can be used to control devices manufactured according to the present disclosure, including passive matrix and active matrix. Many of the devices are intended to be used in a temperature range that is comfortable for humans, such as 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).

[0490] More details regarding OLEDs and the definitions described above can be found in US Patent No. 7,279,704, which is incorporated herein by reference in its entirety.

[0491] The materials and structures described herein can be used in 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.

[0492] In some embodiments, the OLED has one or more characteristics selected from the group consisting of: flexible, rollable, foldable, stretchable, and bendable. In some embodiments, the OLED is transparent or translucent. In some embodiments, the OLED further comprises a layer comprising carbon nanotubes. In some embodiments, the OLED further comprises one or more quantum dots. Such quantum dots can be in the emissive layer or in other functional layers, such as downconversion layers.

[0493] 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 having a diagonal of less than 10 inches or an area of ​​less than 50 square inches. In some embodiments, the OLED is a display panel having a diagonal of at least 10 inches or an area of ​​at least 50 square inches. In some embodiments, the OLED is a lighting panel.

[0494] D. Other materials used in OLED

[0495] The materials described herein serve 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 the device. For example, the emissive dopants disclosed herein can be used by themselves in the EML, or in combination with a wide variety of other emitters, hosts, transport layers, barrier layers, injection layers, electrodes, and other layers that may be present. The materials described or mentioned below are non-limiting examples of materials that can be used in combination with the compounds and devices disclosed herein, and those skilled in the art can readily consult the literature to identify other materials that can be used in combination.

[0496] a) Conductive dopant:

[0497] The charge transport layer can be doped with a conductive dopant to substantially change its charge carrier density, which in turn will change its conductivity. The conductivity is increased by generating charge carriers in the matrix material, and depending on the type of dopant, a change in the Fermi level of the semiconductor can also be achieved. The hole transport layer can be doped with a p-type conductivity dopant, and an n-type conductivity dopant is used in the electron transport layer. In some embodiments, the conductive dopant comprises at least one chemical moiety selected from the group consisting of: a cyano group, a fluorinated aryl or heteroaryl group, a fluorinated alkyl or cycloalkyl group, an alkylene group, a heteroaryl group, an amide, a benzodithiophene, and a highly conjugated heteroaryl group extended by a non-cyclic double bond.

[0498] b)HIL / HTL:

[0499] 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; polymers containing fluorocarbons; polymers having a conductive dopant; conductive polymers such as PEDOT / PSS; self-assembled monomers derived from compounds such as phosphonic acid and silane derivatives; metal oxide derivatives such as MoO x ; p-type semiconducting organic compounds, such as 1,4,5,8,9,12-hexaazatriphenylenehexacarbonitrile; metal complexes; and cross-linkable compounds.

[0500] Examples of aromatic amine derivatives for use in HILs or HTLs include, but are not limited to, the following general structure:

[0501]

[0502] Ar 1 to Ar 9 Each of the following is selected from the group consisting of aromatic hydrocarbon cyclic compounds: benzene, biphenyl, terphenyl, triphenylene, naphthalene, anthracene, phenanthrene, fluorene, pyrene, Perylene and azulene; a group consisting of aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline , quinoxaline, naphthridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine and selenophenodipyridine; and a 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 groups and are bonded to each other directly or via at least one of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, a chain structural unit and an aliphatic ring group. Ar 1 to Ar 9 Each of may be unsubstituted or may be substituted with general substituents as described above, and any two substituents may be joined or fused to form a ring.

[0503] In some embodiments, each Ar 1 to Ar 9 independently comprising a portion selected from the group consisting of:

[0504]

[0505] Where k is an integer from 1 to 20; X 101 to X 108 Is C or N; Z 101 It is C, N, O or S.

[0506] Examples of metal complexes used in HIL or HTL include, but are not limited to, the following general formula:

[0507]

[0508] Wherein Met is a metal with an atomic weight greater than 40; (Y 101 -Y 102 ) is a bidentate ligand, Y 101 and Y 102 The coordinating atoms of L are independently selected from C, N, O, P and S; 101 is another ligand; k' is an integer value from 1 to the maximum number of ligands that can be attached to the metal; and k'+k" is the maximum number of ligands that can be attached to the metal.

[0509] 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 relative + The minimum oxidation potential in solution due to the / Fc coupling is less than about 0.6 V.

[0510] In some embodiments, the HIL / HTL material is selected from the group consisting of: phthalocyanine and porphyrin compounds, starburst triarylamine, CF x Fluorocarbon polymers, conductive polymers (e.g., PEDOT:PSS, polyaniline, polythiophene), phosphonic 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 semiconducting organic complexes, metal organometallic complexes, crosslinkable compounds, polythiophene-based polymers and copolymers, triarylamines, triarylamines containing spirofluorene cores, arylamine carbazole compounds, triarylamines containing (di)benzothiophene / (di)benzofuran, indolocarbazoles, isoindole compounds, and metal carbene complexes.

[0511] c) EBL:

[0512] An electron blocking layer (EBL) can be used to reduce the number of electrons and / or excitons that leave the emissive layer. The presence of such a blocking layer in a device can result in substantially higher efficiency and / or longer lifetime compared to a similar device lacking a blocking layer. In addition, a blocking layer can be used to confine emission to desired areas of the OLED. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and / or higher triplet energy than one or more emitters closest to the EBL interface. In some embodiments, the compound used in the EBL contains at least one carbazole group and / or at least one arylamine group. In some embodiments, the HOMO energy level of the compound used in the EBL is 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.

[0513] d) Subject:

[0514] 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.

[0515] Examples of metal complexes used as hosts preferably have the following general formula:

[0516]

[0517] Wherein Met is a metal; (Y 103 -Y 104 ) is a bidentate ligand, Y 103 and Y 104 The coordinating atoms of L are independently selected from C, N, O, P and S; 101 is another ligand; k' is an integer value from 1 to the maximum number of ligands that can be attached to the metal; and k'+k" is the maximum number of ligands that can be attached to the metal.

[0518] In some embodiments, the metal complex is:

[0519]

[0520] where (ON) is a bidentate ligand with a metal coordinated to O and N atoms.

[0521] In some embodiments, Met is selected from Ir and Pt. In another embodiment, (Y 103 -Y 104 ) is a carbene ligand.

[0522] In some embodiments, the host compound contains at least one selected from the following group: a group consisting of aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenanthrene, fluorene, pyrene, Perylene and azulene; a group consisting of aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, aza -dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, aza-carbazole, aza-indolocarbazole, aza-triphenylene, aza-tetraphenylene, 5λ2-benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, 5,9-dioxa-13b-boronaphtho[3,2,1-de]anthracene; and a group consisting of 2 to 10 cyclic structural units, wherein the cyclic structural units are groups of the same type or different types selected from aromatic hydrocarbon ring groups and aromatic heterocyclic groups and are directly or through 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 may be unsubstituted or may be substituted with a general substituent as described herein or may be further fused.

[0523] In some embodiments, the host compound comprises at least one moiety selected from the group consisting of:

[0524]

[0525] Where k is an integer from 0 to 20 or from 1 to 20. 101 to X 108 Independently selected from C or N. Z 101 and Z 102 are independently selected from C, N, O or S.

[0526] In some embodiments, the host material is selected from the group consisting of: aryl carbazoles, metal 8-hydroxyquinolinols (e.g., alq3, balq), metal phenoxybenzothiazole compounds, conjugated oligomers and polymers (e.g., polyfluorene), aromatic fused rings, zinc complexes, Compounds, aryltriphenylene compounds, poly-fused heteroaryl compounds, donor-acceptor molecules, dibenzofuran / dibenzothiophene compounds, polymers (e.g., PVK), spirofluorene compounds, spirofluorene-carbazole compounds, indolecarbazole, 5-membered electron-deficient heterocycles (e.g., triazole, oxadiazole), tetraphenylene complexes, metal phenoxypyridine compounds, metal coordination complexes (e.g., Zn, Al containing 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 metal organometallic complexes (e.g., metal-carbene complexes).

[0527] e) Emitter materials in EML:

[0528] One or more emitter materials may be used in combination with the compounds or devices of the present disclosure. The emitter material may be emissive or non-emissive in the current device as described herein. Examples of emitter materials are not particularly limited, and any compound may be used as 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.

[0529] In some embodiments, the emitter material has the formula M(L 1 ) x (L 2 ) y (L 3 ) z ;

[0530] Among them L 1 、L 2 and L 3 Can be the same or different;

[0531] where x is 1, 2, or 3;

[0532] where y is 0, 1, or 2;

[0533] where z is 0, 1, or 2;

[0534] Wherein x+y+z is the oxidation state of the metal M;

[0535] Among them L 1 Selected from the group consisting of structures in the following ligand list:

[0536]

[0537]

[0538]

[0539]

[0540] Each L 2 and L 3 Independently selected from the group consisting of structures in the list of ligands in:

[0541] M is selected from the group consisting of Ir, Rh, Re, Ru, Os, Pt, Pd, Zn, Au, Ag, and Cu;

[0542] T is selected from the group consisting of B, Al, Ga and In;

[0543] K 1' is a direct key or is selected from the group consisting of: NR e PR e , O, S and Se;

[0544] Each Y 1 to Y 15 independently selected from the group consisting of carbon and nitrogen;

[0545] Y'Select from the group consisting of: BR e NR e PR e ,O,S,Se,C=O,S=O,SO2,CR e R f 、SiR e R f and GeR e R f ;

[0546] Each R a 、R b 、R c and R d can independently represent monosubstitution to the maximum possible number of substitutions, or no substitution;

[0547] 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 general substituents defined herein; and

[0548] Any two substituents may be fused or joined to form a ring or to form a polydentate ligand.

[0549] In some embodiments, the emitter material is selected from the group consisting of the following dopant group 1:

[0550]

[0551]

[0552]

[0553]

[0554]

[0555]

[0556] in

[0557] X 96 to X 99 Each of is independently C or N;

[0558] Each Y 100 Independently selected from the group consisting of NR", O, S and Se;

[0559] R 10a 、R 20a 、R 30a 、R 40a and R 50a Each of independently represents monosubstitution, up to maximum substitution, or no substitution;

[0560] R, R', R", R 10a 、R 11a 、R 12a 、R 13a 、R 20a 、R 30a 、R 40a 、R 50a 、R 60 、R 70 、R 97 、R 98 and R 99 Each of is independently hydrogen or a substituent selected from the group consisting of general substituents as defined herein; any two substituents may be joined or fused to form a ring.

[0561] In some embodiments, the emitter material is selected from the group consisting of the following dopant group 2:

[0562]

[0563]

[0564]

[0565]

[0566]

[0567]

[0568]

[0569]

[0570] in:

[0571] Each Y 100 Independently selected from the group consisting of NR", O, S and Se;

[0572] L is independently selected from the group consisting of a direct bond, BR", BR"R"', NR", PR", O, S, Se, C=O, C=S, C=Se, C=NR", C=CR"R"', S=O, SO2, CR", CR"R"', SiR"R"', GeR"R"', alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof;

[0573] X 100 and X 200 at each occurrence selected from the group consisting of: O, S, Se, NR" and CR"R"';

[0574] Each R A” 、R B” 、R C” 、R D” 、R E” and R F” independently represents monosubstitution, up to maximum substitution, or no substitution;

[0575] R、R'、R”、R”'、R A1' 、R A2' 、R A” 、R B” 、R C” 、R D” 、R E” 、R F” 、R G” 、R H” 、R I” 、R J” 、R K” 、R L”、R M” and R N” Each of is independently hydrogen or a substituent selected from the group consisting of general substituents as defined herein; any two substituents may be joined or fused to form a ring.

[0576] In some embodiments of the above dopant groups 1 and 2, each unsubstituted aromatic carbon atom may be replaced by N to form an nitrogen heterocycle. In some embodiments, the maximum number of N atoms in a ring is 1 or 2. In some embodiments of the above dopant group 2, each Pt atom in the formula may be replaced by a Pd atom.

[0577] In some embodiments of the OLED, the delayed fluorescent material comprises at least one donor group and at least one acceptor group. In some embodiments, the delayed fluorescent material is a metal complex. In some embodiments, the delayed fluorescent material is a non-metal complex. In some embodiments, the delayed fluorescent material is a Zn, Cu, Ag, or Au complex.

[0578] In some embodiments of OLEDs, the delayed fluorescent material has the formula M(L 5 )(L 6 ), wherein M is Cu, Ag or Au, L 5 and L 6 Different, and L 5 and L 6 Independently selected from the group consisting of:

[0579]

[0580]

[0581]

[0582] Among them A 1 -A 9 are each independently selected from C or N;

[0583] Each R P 、R Q and R U independently represents monosubstitution, up to maximum substitution, or no substitution;

[0584] Each R P 、R P 、R U 、R SA 、R SB 、R RA 、R RB 、R RC 、R RD 、R RE and R RFis independently hydrogen or a substituent selected from the group consisting of general substituents as defined herein; any two substituents may be joined or fused to form a ring.

[0585] In some embodiments of the OLED, the delayed fluorescent material comprises at least one donor moiety selected from the group consisting of:

[0586]

[0587]

[0588] where Y T 、Y U 、Y V and Y W Each is independently selected from the group consisting of B, C, Si, Ge, N, P, O, S, Se, C═O, S═O, and SO2.

[0589] 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 three carbon ring atoms together with their substituents, may be replaced by nitrogen.

[0590] In some embodiments, the delayed fluorescent material comprises at least one acceptor moiety selected from the group consisting of nitrile, isonitrile, borane, fluoride, pyridine, pyrimidine, pyrazine, triazine, aza-carbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, aza-triphenylene, imidazole, pyrazole, oxazole, thiazole, isoxazole, isothiazole, triazole, thiadiazole, and oxadiazole. In some embodiments, the acceptor moiety and the donor moiety as described herein can be directly linked, via a conjugated linker or a non-conjugated linker (e.g., sp 3 carbon or silicon atoms) connected.

[0591] In some embodiments, the fluorescent material comprises at least one chemical moiety selected from the group consisting of:

[0592]

[0593]

[0594]

[0595] where Y F 、Y G 、Y H and Y I Each independently selected from the group consisting of B, C, Si, Ge, N, P, O, S, Se, C=O, S=O, and SO2;

[0596] where XF and X G are each independently selected from the group consisting of C and N.

[0597] 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 three carbon ring atoms together with their substituents, may be replaced by nitrogen.

[0598] f)HBL:

[0599] A hole blocking layer (HBL) can be used to reduce the number of holes and / or excitons that escape the emissive layer. The presence of such a blocking layer in a device can result in substantially higher efficiency and / or longer lifetime compared to a similar device lacking the blocking layer. Furthermore, a blocking layer can be used to confine emission to desired regions of the OLED. In some embodiments, the HBL material has a lower HOMO (further from the vacuum level) and / or higher triplet energy than one or more of the emitters closest to the HBL interface.

[0600] In some embodiments, the compounds used in HBL contain the same molecules or the same functional groups as those used in the subjects described above.

[0601] In some embodiments, the compound used in HBL comprises at least one of the following moieties selected from the group consisting of:

[0602]

[0603] Where k is an integer from 1 to 20; L 101 is another ligand, and k' is an integer from 1 to 3.

[0604] g)ETL:

[0605] The electron transport layer (ETL) may include a material capable of transporting electrons. The electron transport layer may be intrinsic (undoped) or doped. Doping may be used to enhance conductivity. Examples of ETL materials are not particularly limited, and any metal complex or organic compound may be used as long as it is generally used to transport electrons.

[0606] In some embodiments, the compounds used in the ETL comprise at least one of the following moieties in the molecule:

[0607] and fullerenes; wherein 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.

[0608] In some embodiments, the metal complex used in the ETL contains, but is not limited to, the following general formula:

[0609]

[0610] wherein (ON) or (NN) is a bidentate ligand having a metal coordinated to atoms O, N or N,N; L 101 is another ligand; k' is an integer value from 1 to the maximum number of ligands that can be attached to the metal.

[0611] In some embodiments, the ETL material is selected from the group consisting of anthracene-benzimidazole compounds, azatriphenylene derivatives, anthracene-benzothiazole compounds, metal 8-hydroxyquinolinates, metal hydroxybenzoquinolinates, bathocuprine compounds, 5-membered electron-deficient heterocycles (e.g., triazole, oxadiazole, imidazole, benzimidazole), thiol compounds, arylborane compounds, fluorinated aromatic compounds, fullerenes (e.g., C60), triazine complexes, and Zn(N^N) complexes.

[0612] h) Charge Generation Layer (CGL)

[0613] In tandem or stacked OLEDs, the CGL plays a fundamental role in performance. It consists of an n-doped layer and a p-doped layer for injecting electrons and holes, respectively. Electrons and holes are supplied by the CGL and electrodes. Electrons and holes consumed in the CGL are refilled by electrons and holes injected from the cathode and anode, respectively; subsequently, the bipolar current gradually reaches a steady state. Typical CGL materials contain both n- and p-conductivity dopants used in the transport layer.

[0614] In any compound disclosed herein, the hydrogen atom can be partially or completely deuterated. The minimum amount of deuterated hydrogen in the compound is selected from the group consisting of: 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 99% and 100%. As used herein, deuteration percentage has its ordinary meaning and includes the percentage of all possible hydrogens and deuterium atoms replaced by deuterium atoms. In certain embodiments, the deuterium atom is connected to an aromatic ring. In certain embodiments, the deuterium atom is connected to a saturated carbon atom, such as an alkyl or cycloalkyl carbon atom. In some other embodiments, the deuterium atom is connected to a heteroatom, such as a Si or Ge atom.

[0615] 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 present invention. For example, many materials and structures described herein can be replaced with other materials and structures without departing from the spirit of the present invention. Therefore, the present invention as required can include variations of the specific examples and preferred embodiments described herein, as will be apparent to those skilled in the art. It should be understood that the various theories about why the present invention works are not intended to be restrictive.

[0616] Experimental part

[0617] synthesis

[0618]

[0619] II. To a stirred solution of 7-methoxynaphthalene-2-ol I (10.0 g, 1 equivalent, 57.41 mmol) in acetic acid (50.0 mL) and water (10.0 mL) at 0° C. under a nitrogen atmosphere was added aqueous sodium nitrite (4.36 g, 5.00 mL, 1.1 equivalents, 63.15 mmol). The reaction mixture was stirred at 0° C. for 3 hours, diluted with water (50 mL), and the brown precipitate was filtered, washed with water (50 mL), and dried to give 7-methoxy-1-nitrosonaphthalene-2-ol II (10.30 g, 49 mmol, 85%) as a dark brown solid.

[0620] III. To a stirred solution of 7-methoxy-1-nitrosonaphthalene-2-ol II (15.0 g, 1 equivalent, 73.82 mmol) in water (20.0 mL) and ethanol (100 mL) was added zinc (24.13 g, 5 equivalents, 369.1 mmol) and ammonium chloride (39.49 g, 10 equivalents, 738.2 mmol). The reaction mixture was stirred at 40° C. for 16 hours, diluted with EtOAc (50 mL), filtered through a pad of celite, dried over sodium sulfate, and concentrated to afford 1-amino-7-methoxynaphthalene-2-ol III (11.2 g, 55 mmol, 75%) as a yellow solid. The crude material was used directly without any further purification.

[0621] IV. To a stirred solution of 1-amino-7-methoxynaphthalen-2-ol III (11.2 g, 1 equivalent, 55.05 mmol) in EtOAc (100 mL) was added aqueous sodium bicarbonate (13.87 g, 82.57 mL, 2.00 molar concentration, 3 equivalents, 165.1 mmol) and pivaloyl chloride (7.97 g, 8.09 mL, 1.2 equivalents, 66.06 mmol). The reaction mixture was stirred at 25° C. for 3 hours and then diluted with water (150 mL). The organic layer was separated and the aqueous layer was extracted with DCM (2×100 mL), dried over Na 2 SO 4 , and concentrated under reduced pressure. The crude product was purified by silica gel chromatography (220 g column, 0-100% (25% EtOH in EtOAc) / isohexane to afford N-(2-hydroxy-7-methoxynaphthalen-1-yl)pivalamide IV (13.20 g, 46 mmol, 83%) as a sticky colorless gum.

[0622] V. To a stirred solution of N-(2-hydroxy-7-methoxynaphthalen-1-yl)pivalamide IV (13.20 g, 1 eq, 45.88 mmol) in anhydrous toluene (100 mL) was added 4-methylbenzenesulfonic acid hydrate (2.62 g, 0.3 eq, 13.76 mmol) under a nitrogen atmosphere. The reaction mixture was stirred at 110 ° C for 2 hours. The reaction mixture was concentrated under reduced pressure, adsorbed onto silica and purified by silica gel chromatography (220 g column, 0-100% EtOAc / isohexane) to give 2-(tert-butyl)-8-methoxynaphtho[1,2-d]oxazole V (9.300 g, 35 mmol, 75%) as a light yellow solid.

[0623] VI. To a stirred solution of 2-(tert-butyl)-8-methoxynaphtho[1,2-d]oxazole V (9.30 g, 1 equivalent, 34.60 mmol) in anhydrous DCM (50 mL) at 0°C under a nitrogen atmosphere was added BBr3 in DCM (86.51 mL, 1.000 molar concentration, 2.5 equivalents, 86.51 mmol). The reaction mixture was stirred at 0°C for 1 hour. The reaction mixture was warmed to 25°C and stirred for 16 hours. The reaction mixture was poured into ice-cold water (300 mL) and extracted with EtOAc:MeOH. The combined organic layers were washed with saturated NaHCO3 (100 mL), water (100 mL), dried over sodium sulfate, and concentrated under reduced pressure. The crude product was purified by silica gel chromatography (80 g column (dry load), 0-100% EtOAc / isohexane) to afford 2-(tert-butyl)naphtho[1,2-d]oxazol-8-ol VI (7.20 g, 27 mmol, 78%) as an off-white solid.

[0624] VIII. To a stirred solution of 2-(tert-butyl)naphtho[1,2-d]oxazol-8-ol VI (3.97 g, 90 wt%, 1.0 eq, 14.82 mmol) and 4-(2,2-dimethylpropyl-1,1-d2)-2-(2-fluoro-3-nitrophenyl)-5-(methyl-d3)pyridine VII (4.60 g, 99 wt%, 1.0 eq, 14.82 mmol) in anhydrous NMP (50.00 mL) was added potassium carbonate (6.14 g, 3.0 eq, 44.45 mmol) under a nitrogen atmosphere. The reaction mixture was heated to 50° C. for 16 hours, diluted with water (40 mL), and the resulting precipitate was filtered and dried to give a light yellow viscous substance. This was dissolved in MeOH, water was added, and stirred for 10 minutes. The formed precipitate was filtered and dried to give 2-(tert-butyl)-8-(2-(4-(2,2-dimethylpropyl-1,1-d2)-5-(methyl-d3)pyridin-2-yl)-6-nitrophenoxy)naphtho[1,2-d]oxazole VIII (8.70 g, 13 mmol, 91%) as a light brown solid.

[0625] IX. To a stirred solution of 2-(tert-butyl)-8-(2-(4-(2,2-dimethylpropyl-1,1-d2)-5-(methyl-d3)pyridin-2-yl)-6-nitrophenoxy)naphtho[1,2-d]oxazole VIII (9.00 g, 1 eq, 14.64 mmol) in water (18 mL) and ethanol (90 mL) was added zinc (4.79 g, 5 eq, 73.20 mmol) and ammonium chloride (7.83 g, 10 eq, 146.4 mmol). The reaction mixture was stirred at 50 °C for 6 hours. The reaction mixture was diluted with EtOAc (250 mL) and filtered through a pad of celite. The filtrate was dried over Na2SO4, filtered, and concentrated under reduced pressure. The crude compound was redissolved in EtOAc, washed with water (3×100 mL), brine (100 mL), dried over Na 2 SO 4 and concentrated to give 2-((2-(tert-butyl)naphtho[1,2-d]oxazol-8-yl)oxy)-3-(4-(2,2-dimethylpropyl-1,1-d2)-5-(methyl-d3)pyridin-2-yl)aniline IX (7.90 g, 15 mmol, 100%) as an off-white solid.

[0626] X. Sodium nitrite (5.082 g, 5 eq, 73.66 mmol) was added to a mixture of 2-((2-(tert-butyl)naphtho[1,2-d]oxazol-8-yl)oxy)-3-(4-(2,2-dimethylpropyl-1,1-d2)-5-(methyl-d3)pyridin-2-yl)aniline IX (7.90 g, 1 eq, 14.73 mmol) and bromotrichloromethane (5.84 g, 2.91 mL, 2 eq, 29.47 mmol) in DCM (70 mL) and water (70 mL). The mixture was stirred at room temperature for 5 minutes, then acetic acid (16.9 mL, 20 eq, 294.7 mmol) was added. The resulting reaction mixture was stirred at 25 °C for 16 hours, then diluted with DCM (350 mL). The organic layer was separated and washed with saturated NaHCO solution, water (100 mL) and brine (100 mL). The organic layer was dried over NaSO and concentrated. The crude product was purified by silica gel chromatography (220 g column (dry loading), 0-100% EtOAc / isohexane) to give 8-(2-bromo-6-(4-(2,2-dimethylpropyl-1,1-d2)-5-(methyl-d3)pyridin-2-yl)phenoxy)-2-(tert-butyl)naphtho[1,2-d]oxazole X (5.600 g, 9.1 mmol, 61%) as a bright orange solid.

[0627] XI. 8-(2-bromo-6-(4-(2,2-dimethylpropyl-1,1-d2)-5-(methyl-d3)pyridin-2-yl)phenoxy)-2-(tert-butyl)naphtho[1,2-d]oxazole (5.60 g, 1 eq, 8.959 mmol), K2CO3 (3.71 g, 3 eq, 26.88 mmol), pivalic acid (457 mg, 506 μL, 0.5 eq, 4.480 mmol), acetic acid A mixture of palladium (II) (201 mg, 0.1 equivalent, 895.9 μmol), 1,3-bis(2,6-diisopropylphenyl)-1H-imidazole-3-ium chloride (381 mg, 0.1 equivalent, 895.9 μmol) and DMA (2.0 mL) was degassed by evacuation / backfilling with N2 (5 minutes, 3 times), then stirred at 140 ° C for 16 hours, cooled to room temperature, diluted with water (150 mL) and stirred for 30 minutes. The solid was collected by filtration, washed with water (2×50 mL) and dried. The substance was dissolved in DCM and dry loaded onto silica. The crude product was purified by silica gel chromatography (120 g column, 0-100% EtOAc / isohexane) to obtain compound XI as a light pink solid. The solid was dissolved in 25 mL of DCM, MeOH (70 mL) was added and the formed precipitate was settled. The precipitate was filtered and dried to give 2-(tert-butyl)-10-(4-(2,2-dimethylpropyl-1,1-d2)-5-(methyl-d3)pyridin-2-yl)benzofuro[3′,2′:6,7]naphtho[1,2-d]oxazole XI (2.900 g, 5.999 mmol, 66.96%) as a white solid.

[0628] VII. 2-(2-Fluoro-3-nitrophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane XII (20.0 g, 1 eq, 74.89 mmol) and 2-chloro-4-(2,2-dimethylpropyl-1,1-d2)-5-(methyl-d3)pyridine XIII (15.2 g, 1 eq, 74.89 mmol) were dissolved in THF (500 mL) under nitrogen, potassium carbonate (1.5 M in water) (31.05 g, 149.8 mL, 1.500 molar concentration, 3 eq, 224.7 mmol) was added and the mixture was degassed by vacuum / nitrogen cycles. XPhos (1.79 g, 0.05 equivalent, 3.744 mmol) and XPhosPd(crotyl)Cl (2.52 g, 0.05 equivalent, 3.744 mmol) were added and the reaction mixture was further degassed by vacuum / nitrogen circulation. The mixture was heated to 50° C. for 0.5 hours. The mixture was diluted with EtOAc (200 mL) and water (100 mL). The aqueous layer was extracted with EtOAc (2×50 mL). The combined organic extracts were washed with brine (200 mL), dried over Na SO , filtered and concentrated in vacuo. The crude product was purified by silica gel chromatography (220 g column (dry load), 0-100% EtOAc / isohexane) to afford 4-(2,2-dimethylpropyl-1,1-d2)-2-(2-fluoro-3-nitrophenyl)-5-(methyl-d3)pyridine (21.9 g, 71 mmol, 94%) as a pale green solid.

[0629]

[0630] Compound 1. A 250 mL 4-necked flask was equipped with a stirring bar, a thermocouple, and a condenser and charged with XIV, 2-(tert-butyl)-10-(4-(2,2-dimethylpropyl-1,1-d2)-5-(methyl-d3)pyridin-2-yl)benzofuro[3',2':6,7]naphtho[1,2-d]oxazole XI (1.458 g, 1.00 equiv, 3.027 mmol), acetone (75.67 mL), and triethylamine (918.8 mg, 3.00 equiv, 9.080 mmol). The reaction was heated to 50° C. After 10 hours, the reaction was cooled to room temperature and then concentrated under reduced pressure. The orange solid was triturated in dichloromethane / methanol (100 mL) at 35° C. for 1 hour. Once at room temperature, the mixture was filtered and the resulting solid (2.27 g) was dried under vacuum. Into a 500mL round-bottom flask, solid and 260mL THF were loaded. The solution was bubbled with N2 and heated to 80°C for 30 minutes under 456nm radiation. The solvent was removed in vacuo. The crude material was passed through a basic alumina column eluted with dichloromethane, and the solution was concentrated in vacuo. The crude material was then purified by silica gel chromatography eluted with 30-100% toluene / hexane. The product fractions were concentrated on a rotary evaporator. The resulting material was ground with dichloromethane / methanol, and the resulting solid was filtered, rinsed with methanol and dried in vacuo to produce compound 1 of the present invention (1.70g, 51% yield).

[0631] Through high vacuum (<10 -7 All device examples were made by VTE (Vortex Thermal Evaporation). The anode is The cathode is made of indium tin oxide (ITO). LiF and All devices were immediately packaged in a nitrogen glove box (<1 ppm H2O and O2) with epoxy-sealed glass lids after fabrication, and a moisture absorber was incorporated into the packaging.

[0632] The organic stack of the device example consists of the following materials in order from the ITO surface: HATCN as hole injection layer (HIL), Hole transport material HTM as hole transport layer (HTL), The EBM acts as an electron blocking layer (EBL), H1 doped with 30wt% H2 and 5wt% emitter as the emission layer (EML), H2 as a barrier layer (BL), and 35% ETM in Liq (8-hydroxyquinoline lithium) as electron transport layer (ETL). As used herein, HATCN, HTM, EBL, H1, H2 and ETM have the following structures:

[0633]

[0634] During manufacturing, the device was tested to measure EL and JVL. To do this, a 2-channel Keysight B2902ASMU was used with a current of 10 mA / cm 2 The sample was energized with a current density of 100 nm and measured using a Photo Research PR735 spectroradiometer. The radiance (W / str / cm 2 ) and total integrated photon counts. The device was then placed under a large area silicon photodiode for JVL scanning. The device was operated at 10 mA / cm 2 The integrated photon count under is used to convert the photodiode current into photon counts. The voltage is swept from 0 to 200 mA / cm 2 The external quantum efficiency (EQE) of the device was calculated using total integrated photon counting. All results are summarized in the table below, where the EQE is calculated at a current density of 10 mA / cm 2 When reported as relative values, these values ​​have been normalized to the results of the comparative example (device 2).

[0635] Table 1

[0636]

[0637] Table 1 summarizes the performance of electroluminescent devices of the present invention containing a fused oxazole ring on its luminescent ligand and a comparative device having a benzene ring in this position. Both devices exhibited emission with a peak wavelength in the 520-525 nm range, however, the present device exhibited a significantly narrower emission lineshape than the comparative device. Typically, the FWHM of phosphorescent emitter complexes is wide. Achieving a narrow FWHM has been a long-sought goal. The narrower the FWHM, the better the color purity for display applications. As background information, the ideal lineshape is a single wavelength (single line). As can be seen here, the present compounds having a terminal 5-membered ring on moiety B can reduce the FWHM by 33% compared to the comparative compound in which moiety B has a terminal benzene ring. In previous OLED research, lineshape narrowing was achieved slowly, nanometer by nanometer, but here we were able to reduce the FWHM by 33% by simply changing the terminal ring of moiety B. This is a very unexpected result, exceeding any value that can be attributed to experimental error.

Claims

1. A compound having a first ligand L comprising a structure of Formula I A : wherein the moiety A 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; wherein moiety B is a polycyclic fused ring system consisting of at least five 5-membered or 6-membered carbocyclic or heterocyclic rings, at least one of which is a 5-membered ring; wherein the at least one 5-membered ring of portion B comprises ring atoms selected from the group consisting of C, N, O, Si, S, Se, and Ge; the at least one 5-membered ring of portion B is fused to exactly one other ring; and the at least one 5-membered ring of portion B is not joined to M by a direct bond; where Z 1 -Z 4 are each independently C or N; Among them L 1 Selected from the group consisting of: direct bond, O, S, Se, NR, BR, BRR', PR, CR, C=O, C=NR, C=CRR', C=S, CRR', SO, SO2, P(O)R, SiRR' and GeRR'; where K 1 and K 2 Each independently selected from the group consisting of: direct bond, O, S, N (R α )、P(R α )、B(R α )、C(R α )(R β ) and Si(R α )(R β ); where R A and R B Each independently represents monosubstituted to the maximum permissible substitution, or no substitution; in represents a single bond or a double bond; Where each R, R', R α 、R β 、R A and R B is independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, germanyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof; Among them L A Coordinate with metal M; wherein the metal M is selected from the group consisting of Ir, Rh, Re, Ru, Os, Pt, Pd, Ag, Au and Cu; Wherein M can coordinate with other ligands; Among them L A can be joined with other ligands to form tridentate, tetradentate, pentadentate, or hexadentate ligands; and Any two substituents may be joined or fused to form a ring.

2. The compound according to claim 1, wherein R, R', R α 、R β 、R A and R B Each of the groups is independently hydrogen or a substituent selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silanyl, germanyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thio, and combinations thereof; and / or wherein L 1 is a direct key; and / or wherein Z 1 -Z 4 exactly one of them is N; and / or K 1 and K 2 One of them is a direct key.

3. The compound according to claim 1, wherein moiety B comprises exactly five fused 5- or 6-membered rings; and / or wherein moiety B comprises at least one 5-membered heterocyclic ring comprising at least two different heteroatoms; and / or wherein M is Ir.

4. The compound according to claim 1, wherein the ligand L A Selected from the group consisting of the following structures as defined in Listing 1 as defined herein; wherein each Y1-Y5 is independently selected from the group consisting of: O, S, Se, NR, BR, BRR', PR, CR, C=O, C=NR, C=CRR', C=S, CRR', SO, SO2, P(O)R, SiRR' and GeRR'; X1-X 12 Each of is independently C or N; The remaining variables are the same as defined previously; Any two substituents may be optionally joined or fused to form a ring.

5. The compound according to claim 1, wherein the ligand L A Selected from the group consisting of the following structures as defined in Listing 2 as defined herein; where R AA and R BB Each independently represents monosubstituted to the maximum permissible substitution, or no substitution; Each R AA and R BB are independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, germanyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof; and Any two substituents may be optionally joined or fused to form a ring.

6. The compound according to claim 1, wherein the first L A Select from the group consisting of: L Ai (R J )(R K )(R L )(Y M ), where i is an integer from 1 to 111, R J 、R K and R L Each of is independently selected from V1 to V148; and Y M selected from Y1 to R12; and L A 1-(V1)(V1)(V1)(Y1) to L A 111-(V148)(V148)(V148)(Y12), and L A 1-(R1)(R1)(R1)(Y1) to L A Each of 111-(V148)(V148)(V148)(Y12) is defined in Listing 3 as defined herein; wherein V1 to V148 have the structure as defined in Listing 7 as defined herein; where Y1 to Y12 have the following structure 7. The compound according to claim 1, wherein the compound has M(L A ) p (L B ) q (L C ) r The formula, where L B and L C each is a bidentate ligand; and wherein p is 1, 2, or 3; q is 0, 1, or 2; r is 0, 1, or 2; And p+q+r is the oxidation state of the metal M.

8. The compound according to claim 7, wherein L B and L C each independently selected from the group consisting of the following structures of Listing 4 as defined herein; in: T is selected from the group consisting of B, Al, Ga and In; K 1 'Selected from the group consisting of: single bond, O, S, NR e PR e BR e , CR e R f and SiR e R f ; Y 1 to Y 13 Each of is independently selected from the group consisting of C and N; Y' is selected from the group consisting of: BR e BR e R f NR e PR e 、P(O)R e 、O、S、Se、C=O、 C=S, C=Se, C=NR e , C=CR e R f , S=O, SO2, CR e R f , SiR e R f and GeR e R f ; R e and R f may be fused or joined to form a ring; Each R a 、R b 、R c and R d independently represents monosubstitution to the maximum allowed number of substitutions, or no substitution; R a1 、R b1 、R c1 、R d1 、R a 、R b 、R c 、R d 、R e and R f each of which is independently hydrogen or a substituent selected from the group consisting of deuterium, halo, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, germanyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, selenanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and R a1 、R b1 、R c1 、R d1 、R a 、R b 、R c and R d Any two substituents of may be fused or joined to form a ring or to form a multidentate ligand.

9. The compound of claim 7, wherein the compound is selected from the group consisting of the structures in List 9 as defined herein.

10. The compound of claim 7, wherein the compound comprises a structure of Formula II: in: M 1 is Pd or Pt; Moieties E and F are each independently a monocyclic or polycyclic fused ring system, wherein each ring in said monocyclic or polycyclic fused ring system is independently a 5- to 10-membered carbocyclic or heterocyclic ring; Z 5 and Z 6 are each independently C or N; K 1 , K 2 , K 3 and K 4 Each independently selected from the group consisting of: direct bond, O, S, N (R α )、P(R α )、B(R α )、C(R α )(R β ) and Si(R α )(R β ), wherein at least two of them are direct bonds; L 2 , L 3 and L 4 Each independently does not exist or is selected from the group consisting of: direct key, BR, BRR', NR, PR, P(O)R, O, S, Se, C=O, C=S, C=Se, C=NR, C=CRR', S=O, SO2, CR, CRR', SiRR', GeRR', alkylene, cycloalkyl, aryl, cycloalkylene, arylene, heteroarylene, and combinations thereof, wherein L is present 3 and L 4 at least one of; R E and R F Each independently represents zero substitution, monosubstitution, or up to the maximum allowed number of substitutions on its associated ring; R α 、R β , R', R", R E and R F each of which is independently hydrogen or a substituent selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silanyl, germanyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thio, and combinations thereof; Where chemically feasible, two adjacent R A 、R B 、R C 、R E and R F may be joined or fused together to form a ring; and Z 1 -Z 4 , L 1 、R A 、R B , Part A and Part B are all defined the same as above.

11. The compound according to claim 10, wherein the compound is selected from the group consisting of compounds having the formula Pt(L A' )(Ly) is a group of compounds: Among them L A' selected from the group consisting of the structures shown below in Listing 10 as defined herein; Each R A ' and R B ' is independently hydrogen or selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, germanyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thiol, sulfinyl, sulfonyl, phosphino, and combinations thereof; L 1 -L 4 Each of is independently a direct bond or is selected from the group consisting of: O, S, Se, NR, BR, BRR', PR, CR, C=O, C=NR, C=CRR', C=S, CRR', SO, SO2, P(O)R, SiRR' and GeRR'; The remaining variables are the same as defined previously; Among them L y selected from the group consisting of the structures shown below in Listing 11 as defined herein; where R X and R Y are independently hydrogen or selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, germanyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thiol, sulfinyl, sulfonyl, phosphino, and combinations thereof; The remaining variables are the same as defined previously.

12. An organic light-emitting device (OLED), comprising: anode; cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises a ligand L A The compound, the ligand L A Comprising the structure of Formula I: wherein the moiety A 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; wherein moiety B is a polycyclic fused ring system consisting of at least five 5-membered or 6-membered carbocyclic or heterocyclic rings, at least one of which is a 5-membered ring; wherein the at least one 5-membered ring of portion B comprises ring atoms selected from the group consisting of C, N, O, Si, S, Se, and Ge; the at least one 5-membered ring of portion B is fused to exactly one other ring; and the at least one 5-membered ring of portion B is not joined to M by a direct bond; where Z 1 -Z 4 are each independently C or N; Among them L 1 Selected from the group consisting of: direct bond, O, S, Se, NR, BR, BRR', PR, CR, C=O, C=NR, C=CRR', C=S, CRR', SO, SO2, P(O)R, SiRR' and GeRR'; where K 1 and K 2 Each independently selected from the group consisting of: direct bond, O, S, N (R α )、P(R α )、B(R α )、C(R α )(R β ) and Si(R α )(R β ); where R A and R B Each independently represents monosubstituted to the maximum permissible substitution, or no substitution; in represents a single bond or a double bond; Where each R, R', R α 、R β 、R A and R B is independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, germanyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof; Among them L A Coordinate with metal M; wherein the metal M is selected from the group consisting of Ir, Rh, Re, Ru, Os, Pt, Pd, Ag, Au and Cu; Wherein M can coordinate with other ligands; Among them L A can be joined with other ligands to form tridentate, tetradentate, pentadentate, or hexadentate ligands; and Any two substituents may be joined or fused to form a ring.

13. The OLED of claim 12 , wherein the organic layer further comprises a host, wherein the host comprises at least one chemical moiety selected from the group consisting of triphenylene, carbazole, indolocarbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, 5λ2-benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, 5,9-dioxa-13b-borazinonaphtho[3,2,1-de]anthracene, triazine, aza-triphenylene, aza-carbazole, aza-indolocarbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, aza-5λ2-benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, and aza-(5,9-dioxa-13b-borazinonaphtho[3,2,1-de]anthracene).

14. The OLED of claim 13, wherein the host is selected from the group consisting of the structures in List 17 as defined herein; in: Each of J1 to J6 is independently C or N; L' is a direct bond or an organic linking group; Each Y AA 、Y BB 、Y CC and Y DD independently selected from the group consisting of: absence of bond, direct bond, O, S, Se, CRR', SiRR', GeRR', NR, BR, BRR'; R A '、R B '、R C '、R D '、R E '、R F ' and R G Each of ' independently represents monosubstitution, up to maximum substitution, or no substitution; Each R, R', R A '、R B '、R C '、R D '、R E '、R F ' and R G ' is independently hydrogen or a substituent selected from the group consisting of general substituents as defined herein; any two substituents may be joined or fused to form a ring; Also, where possible, each unsubstituted aromatic carbon atom is optionally replaced with N to form an aza-substituted ring.

15. A consumer product comprising an organic light emitting device (OLED), the OLED comprising: anode; cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises a ligand L A The compound, the ligand L A Comprising the structure of Formula I: wherein the moiety A 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; wherein moiety B is a polycyclic fused ring system consisting of at least five 5-membered or 6-membered carbocyclic or heterocyclic rings, at least one of which is a 5-membered ring; wherein the at least one 5-membered ring of portion B comprises ring atoms selected from the group consisting of C, N, O, Si, S, Se, and Ge; the at least one 5-membered ring of portion B is fused to exactly one other ring; and the at least one 5-membered ring of portion B is not joined to M by a direct bond; where Z 1 -Z 4 are each independently C or N; Among them L 1 Selected from the group consisting of: direct bond, O, S, Se, NR, BR, BRR', PR, CR, C=O, C=NR, C=CRR', C=S, CRR', SO, SO2, P(O)R, SiRR' and GeRR'; where K 1 and K 2 Each independently selected from the group consisting of: direct bond, O, S, N (R α )、P(R α )、B(R α )、C(R α )(R β ) and Si(R α )(R β ); where R A and R B Each independently represents monosubstituted to the maximum permissible substitution, or no substitution; in represents a single bond or a double bond; Where each R, R', R α 、R β 、R A and R B is independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, germanyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof; Among them L A Coordinate with metal M; wherein the metal M is selected from the group consisting of Ir, Rh, Re, Ru, Os, Pt, Pd, Ag, Au and Cu; Wherein M can coordinate with other ligands; Among them L A can be joined with other ligands to form tridentate, tetradentate, pentadentate, or hexadentate ligands; and Any two substituents may be joined or fused to form a ring.

Images