Organic electroluminescent materials and devices

Abstract

The invention relates to organic electroluminescent materials and devices. There is provided a compound comprising a first ligand LA of Formula I: # imgabs0 # in Formula I, each of X1 to X7 is C or N; k1 is a direct bond or a linking group; r1 and R2 are substituents; each R3, R4, R5, R alpha, R beta, RA, RB and RC is hydrogen or a universal substituent as defined herein; lA is coordinated with metal M; when R1 is a substituted or unsubstituted aryl group, specific conditions must be satisfied, and when R1 is an alkyl group, other conditions must be satisfied. Formulations, OLEDs, and consumer products containing the compounds are also provided.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority under 35 U.S.C. §119(e) to U.S. Provisional Application Nos. 63 / 508,822 (filed on June 16, 2023), 63 / 509,867 (filed on June 23, 2023), and 63 / 607,289 (filed on December 7, 2023), and the entire contents of all of the above-mentioned applications are incorporated herein by reference. Technical Field

[0003] The present disclosure relates generally to organic or metal coordination compounds and formulations and various uses thereof, including use 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 desirable. Many materials used to manufacture such devices are relatively cheap, so organic optoelectronic devices have the potential for 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 manufacturing 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 voltage is applied across the device. OLEDs are becoming an increasingly attractive technology in applications such as displays, lighting, and backlighting.

[0006] One application of emissive molecules is full-color displays. Industry standards for such displays require pixels suitable for emitting 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, an absorption filter is 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 well known in the art. Summary of the invention

[0007] In one aspect, the present disclosure provides a first ligand L comprising formula I A Compounds: in

[0008] X1 To X 7 each independently is C or N;

[0009] K 1 Selected from the group consisting of: direct key, O, S, N(R α )、P(R α )、B(R α )、C(R α )(R β ) and Si(R α )(R β );

[0010] R A , R B and R C Each of the above independently represents a single substitution to the maximum number of substitutions allowed, or no substitution;

[0011] Each R 1 and R 2 are independently substituents selected from the group consisting of halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boryl, aralkyl, alkoxy, aryloxy, amino, silyl, germyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thiol, sulfinyl, sulfonyl, phosphino, selenoalkyl, and combinations thereof;

[0012] Each R 3 , R 4 , R 5 , R α , R β , R A , R B and R C are independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boryl, aralkyl, alkoxy, aryloxy, amino, silanyl, germanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thiol, sulfinyl, sulfonyl, phosphino, selenanyl, and combinations thereof;

[0013] L A Coordinate with metal M;

[0014] M is selected from the group consisting of Ru, Os, Ir, Pd, Pt, Cu, Ag and Au;

[0015] L A Can be combined with other ligands to form tridentate, tetradentate, pentadentate or hexadentate ligands;

[0016] Any two substituents may be joined or fused to form a ring;

[0017] When R 1 is substituted or unsubstituted aryl, at least one of the following statements is true:

[0018] 1.R 1 Contains fused rings,

[0019] 2.R 2 is a substituted aryl group and contains a fused ring,

[0020] 3. At least one R A Not hydrogen,

[0021] 4.R 2 It is Formula II: And (i) R 3 With R 4 Different, (ii) R 5 is not hydrogen, or (iii) both conditions (i) and (ii), and

[0022] 5.R 2 is Formula II, R 3 is phenyl or d 5 -phenyl, and R 3 With R 4 different; and

[0023] When R 1 is an alkyl group, at least one of the following statements is true:

[0024] a 2 is Formula II, R 3 is not hydrogen or 3,5-di-tert-butylphenyl, and R 3 With R 4 different,

[0025] B R 2 is Formula II and R 5 is not hydrogen, and

[0026] C 1 With R 2 Fused together.

[0027] In another aspect, the present disclosure provides a formulation comprising a ligand L having Formula I as described herein A of compounds.

[0028] In yet another aspect, the present disclosure provides an OLED having an organic layer comprising a ligand L having Formula I as described herein. A of compounds.

[0029] In yet another aspect, the present disclosure provides a consumer product comprising an OLED having an organic layer comprising a ligand L having Formula I as described herein. A of compounds. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 An organic light emitting device is shown.

[0031] Figure 2 An inverted organic light-emitting device without a separate electron transport layer is shown. DETAILED DESCRIPTION

[0032] A. Terminology

[0033] Unless otherwise stated, the following terms used herein are defined as follows:

[0034] As used herein, "top" means farthest from the substrate, while "bottom" means closest to the substrate. When a first layer is described as being "placed "above" a second layer, the first layer is placed farther from the substrate. Unless it is specified that the first layer is "in contact with" the second layer, there may be other layers between the first layer and the second layer. For example, a cathode may be described as being "placed "above" an anode, even though there are various organic layers between the two.

[0035] 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.

[0036] 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 the ionization potential (IP) is measured as a negative energy relative to the vacuum energy level, a higher HOMO energy level corresponds to an IP with a smaller absolute value (less negative IP). Similarly, a higher LUMO energy level corresponds to an electron affinity (EA) with a smaller absolute value (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.

[0037] As used herein, and as will be generally understood by one 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 farther in the downward direction from the vacuum level. Thus, the definition of HOMO and LUMO energy levels follows different rules than work functions.

[0038] 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 light of a particular color may include one or more emissive layers disposed on top of each other in a stacked manner.

[0039] As used herein, a "NIR," "red," "green," "blue," or "yellow" layer, material, region, or device refers to a layer, material, region, or device that emits light in a wavelength range of about 700-1500 nm, 580-700 nm, 500-600 nm, 400-500 nm, or 540-600 nm, respectively, or a layer, material, region, or device having the highest emission spectrum peak in the corresponding wavelength region. In some arrangements, separate regions, layers, materials, or devices may provide separate "deep blue" and "light blue" emissions. As used herein, a "deep blue" emission component refers to an emission having a peak emission wavelength that is at least about 4 nm less than the peak emission wavelength of a "light blue" emission component. Typically, the peak emission wavelength of the "light blue" emission component is in the range of about 465-500 nm, and the peak emission wavelength of the "deep blue" emission component is in the range of about 400-470 nm, but these ranges may vary for some configurations.

[0040] In some arrangements, a color change layer is provided that converts, modifies or changes the color of light emitted by another layer to an emission having a different wavelength. The color change layer may be formulated to shift the wavelength of light emitted by another layer by a specified amount, the amount being measured by the difference between the wavelength of the emitted light and the wavelength of the resulting light. In general, there are two types of color change layers: color filter layers that modify the spectrum by removing light of non-desired wavelengths, and color-changing layers that convert higher energy photons into lower energy. For example, there may be a "red" color filter layer to filter the input light to remove light with wavelengths outside the range of about 580-700nm. A "color" component refers to a component that, when activated or used, produces or otherwise emits light having a specific color as previously described. For example, a "first emission region of a first color" and a "second emission region of a second color different from the first color" describe two emission regions that, when activated within the device, emit two different colors as previously described.

[0041] As used herein, emissive materials, layers, and regions may be different from each other and from other structures based on the light that the material, layer, or region initially produces as opposed to the light that the same or different structure ultimately emits. Initial light generation is typically the result of a change in energy levels that results in photon emission. For example, an organic emissive material may initially produce blue light, which may be converted to red or green light by a color filter, quantum dots, or other structure, such that the complete emissive stack or sub-pixel emits red or green light. In this case, the initial emissive material, region, or layer may be referred to as the "blue" component, even if the sub-pixel is the "red" or "green" component.

[0042] In some cases, it may be preferred to describe the color of a component (e.g., 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 within or near the edge of the "green" region and one within or near the edge of the "red" region, as previously described. Accordingly, as used herein, each color term also corresponds to a shape in the 1931 CIE coordinate color space. A shape in the 1931 CIE color space is constructed by tracing the trajectory between two color points and any other internal points. For example, the internal shape parameters for red, green, blue, and yellow may be defined as follows:

[0043]

[0044] In some instances, the terms "halo," "halogen," or "halo" are used interchangeably and refer to fluoro, chloro, bromo, and iodo.

[0045] The term "acyl" refers to a substituted carbonyl (-C(O)-R s ).

[0046] The term "ester" refers to a substituted oxycarbonyl (-OC(O)-R s OR-C(O)-OR s ) group.

[0047] The term "ether" refers to -OR s Group.

[0048] The terms "thio" or "thioether" are used interchangeably and refer to -SR s Group.

[0049] The term "selenoalkyl" refers to -SeR s Group.

[0050] The term "sulfinyl" refers to -S(O)-R s Group.

[0051] The term "sulfonyl" refers to -SO2-Rs Group.

[0052] 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.

[0053] The term "silyl group" refers to a group containing at least one silicon atom bonded to the associated structure. 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.

[0054] The term "germanyl" refers to a group containing at least one germanium atom bonded to an associated 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.

[0055] The term "boryl" refers to a group containing at least one boron atom bonded to the structure of interest. 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.

[0056] In each of the above, R s It may be hydrogen or a substituent selected from the group consisting of general substituents defined in the present 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.

[0057] 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 one to fifteen carbon atoms, preferably one to nine carbon atoms, and include methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, and the like. In addition, the alkyl group may be further substituted.

[0058] The term "cycloalkyl" refers to and includes monocyclic, polycyclic and spirocycloalkyl groups having cycloalkyl carbon atoms bonded to the related structure. Preferred cycloalkyl groups are cycloalkyl groups 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.

[0059] The term "heteroalkyl" or "heterocycloalkyl" refers to an alkyl or cycloalkyl group having at least one carbon atom replaced by a heteroatom, respectively. Optionally, at least one heteroatom is selected from O, S, N, P, B, Si, Ge and Se, preferably O, S or N. In addition, the heteroalkyl or heterocycloalkyl group may be further substituted.

[0060] The term "alkenyl" refers to and includes both straight and branched olefin groups. Alkenyl is essentially an alkyl group including at least one carbon-carbon double bond in the alkyl chain, wherein one carbon atom from the carbon-carbon double bond is bonded to a related structure. Cycloalkenyl is essentially a cycloalkyl group including 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, alkenyl, cycloalkenyl or heteroalkenyl groups may be further substituted.

[0061] The term "alkynyl" refers to and includes both straight 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 from the carbon-carbon triple bond is bonded to the associated structure. Preferably, the alkynyl group is an alkynyl group containing two to fifteen carbon atoms. In addition, the alkynyl group may be further substituted.

[0062] 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.

[0063] The term "heterocyclic group" refers to and includes aromatic and non-aromatic cyclic groups containing at least one heteroatom. Optionally, at least one heteroatom is selected from O, S, Se, N, P, B, Si, Ge and Se, preferably O, S, N or B. Heteroaromatic cyclic 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, etc., and cyclic ethers / thioethers, such as tetrahydrofuran, tetrahydropyran, tetrahydrothiophene, etc. In addition, the heterocyclic group can be further substituted or fused.

[0064] The term "aryl" refers to and includes both monocyclic and polycyclic aromatic hydrocarbon groups. Polycyclics may have two or more rings in which two carbons are common to two adjacent rings (the rings are "fused"). Preferred aryl groups are those containing six to thirty carbon atoms, preferably six to twenty-four carbon atoms, six to eighteen carbon atoms, and more preferably six to twelve carbon atoms. Particularly preferred are aryl groups having six carbons, ten carbons, twelve carbons, fourteen carbons, or eighteen carbons. Suitable aryl groups include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenanthrene, phenanthrene, 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.

[0065] 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 one to six heteroatoms. Polycyclic heterocyclic ring systems may have two or more aromatic rings, wherein two atoms are common to two adjacent rings (the rings are "fused"), wherein at least one of the rings is a heteroaryl. Heteropolycyclic aromatic ring systems may have one to six heteroatoms in each ring of the polycyclic aromatic ring system. Preferred heteroaryls are heteroaryls containing three to thirty carbon atoms, preferably three to twenty-four carbon atoms, three to eighteen carbon atoms, and more preferably three to twelve carbon atoms. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridyl indole, pyrrolobipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzo Imidazole, indazole, indole oxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, dibenzopyran, acridine, phenazine, phenothiazine, phenoxazine, benzofuranopyridine, furanodipyridine, 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-boranaphtho[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.

[0066] 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 -benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, 5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene, and their respective aza analogs are of particular interest.

[0067] 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, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, seleno, sulfinyl, sulfonyl, phosphino, and combinations thereof.

[0068] In some cases, preferred universal substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silanyl, germanyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thio, and combinations thereof.

[0069] In some cases, more preferred universal substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, alkoxy, aryloxy, amino, silanyl, germanyl, boronyl, aryl, heteroaryl, nitrile, thio, and combinations thereof.

[0070] In some cases, even more preferred universal substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, silane, aryl, heteroaryl, nitrile, and combinations thereof.

[0071] In still other cases, the most preferred universal substituents are selected from the group consisting of deuterium, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0072] The terms "substituted" and "substituted" refer to the bonding of a substituent other than H to the relevant position, such as carbon or nitrogen. For example, when R 1 When it represents a single substitution, then one R 1 must not be H (i.e. substituted). Similarly, when R 1 When it indicates disubstituted, the two R 1 must not be H. Similarly, when R 1 When it indicates zero substitution or no substitution, R 1 This can be, for example, hydrogen with available valences for the ring atoms, such as the carbon atoms of benzene and the nitrogen atoms in pyrrole, or simply none for ring atoms with full 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 in the ring atoms.

[0073] As used herein, "combinations thereof" means that one or more members of the applicable list are combined to form known or chemically stable arrangements that can be envisioned by a person of ordinary skill in the art from the applicable list. For example, alkyl groups can be combined with deuterium to form partially or completely deuterated alkyl groups; halogens can be combined with alkyl groups to form halogenated alkyl substituents; and halogens, alkyl groups, and aryls can be combined to form halogenated arylalkyl groups. In one case, the term substitution includes a combination of two to four of the listed groups. In another case, the term substitution includes a combination of two to three groups. In yet another case, the term substitution includes a combination of two groups. Preferred combinations of substituents are substituents containing up to fifty atoms that are not hydrogen or deuterium, or substituents including up to forty atoms that are not hydrogen or deuterium, or substituents including up to thirty atoms that are not hydrogen or deuterium. In many cases, preferred combinations of substituents will include up to twenty atoms that are not hydrogen or deuterium.

[0074] The "aza" designations in the fragments described herein, i.e., azadibenzofuran, azadibenzothiophene, etc., mean that one or more CH groups in the respective aromatic rings may be replaced by a nitrogen atom, for example and without any limitation, azatriphenylene encompasses dibenzo[f,h]quinoxaline and dibenzo[f,h]quinoline. Other nitrogen analogs of the aza-derivatives described above can be readily envisioned by one of ordinary skill in the art, and all such analogs are intended to be encompassed by the term as set forth herein.

[0075] 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 (all of which are incorporated herein by reference in their entirety) describe the preparation of organometallic complexes substituted with deuterium. Reference is also made to Ming Yan et al., Tetrahedron, 2015, 71, 1425-30 and Atzrodt et al., Angew. Chem. Int. Ed. (Review) 2007, 46, 7744-65, which are incorporated herein by reference in their entirety, which respectively describe the deuteration of methylene hydrogens in benzylamines and the efficient pathways for replacing aromatic ring hydrogens with deuterium.

[0076] As used herein, any specific listed substituents, such as (but not limited to) methyl, phenyl, pyridyl, etc., include their non-deuterated, partially deuterated, and fully deuterated forms. Similarly, substituent categories (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 chemical structures whose valences are not fully filled by H or D should be deemed to include their non-deuterated, partially deuterated, and fully deuterated forms. For example, The chemical structure of 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.

[0077] 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 a whole molecule (e.g., benzene, naphthalene, dibenzofuran). As used herein, these different ways of naming substituents or attaching fragments are considered equivalent.

[0078] 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 in which 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 2,2' positions in biphenyl or 1,8 positions in naphthalene).

[0079] B. Compounds of the Disclosure

[0080] In one aspect, the present disclosure provides a first ligand L comprising formula I A Compounds: in:

[0081] X 1 To X 7 each independently is C or N;

[0082] K 1 Selected from the group consisting of: direct key, O, S, N(R α )、P(R α )、B(R α )、C(R α )(R β ) and Si(R α )(R β);

[0083] R A , R B and R C Each of the above independently represents a single substitution to the maximum number of substitutions allowed, or no substitution;

[0084] Each R 1 and R 2 are independently substituents selected from the group consisting of halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boryl, aralkyl, alkoxy, aryloxy, amino, silyl, germyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thiol, sulfinyl, sulfonyl, phosphino, selenoalkyl, and combinations thereof;

[0085] Each R 3 , R 4 , R 5 , R α , R β , R A , R B and R C is independently hydrogen or a substituent selected from the group consisting of general substituents defined herein;

[0086] L A Coordinate with metal M;

[0087] M is selected from the group consisting of Ru, Os, Ir, Pd, Pt, Cu, Ag and Au;

[0088] L A Can be combined with other ligands to form tridentate, tetradentate, pentadentate or hexadentate ligands;

[0089] Any two substituents may be joined or fused to form a ring;

[0090] When R 1 is substituted or unsubstituted aryl, at least one of the following statements is true:

[0091] 1.R 1 Contains fused rings,

[0092] 2.R 2 is a substituted aryl group and contains a fused ring,

[0093] 3. At least one R A Not hydrogen,

[0094] 4.R 2 It is Formula II: And (i) R 3 With R 4 Different, (ii) R5 is not hydrogen, or (iii) both conditions (i) and (ii), and

[0095] 5.R 2 is Formula II, R 3 is phenyl or d 5 -phenyl, and R 3 With R 4 different; and

[0096] When R 1 is an alkyl group, at least one of the following statements is true:

[0097] a 2 is Formula II, R 3 is not hydrogen or 3,5-di-tert-butylphenyl, and R 3 With R 4 different,

[0098] B R 2 is Formula II and R 5 is not hydrogen, and

[0099] C 1 With R 2 Fused together.

[0100] In some embodiments, R 1 , R 2 , 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 Partially or completely deuterated. In some embodiments, at least R 1 is partially or fully deuterated. In some embodiments, at least R 2 is partially or fully deuterated.

[0101] In some embodiments, each R 1 and R 2 is independently a substituent selected from the group consisting of fluoro, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silanyl, germanyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thio, and combinations thereof;

[0102] Each R 3 , R 4 , R 5 , R α , R β , R A and R Bis independently hydrogen or a substituent selected from the group consisting of preferred general substituents defined herein.

[0103] In some embodiments, each R 1 and R 2 is independently a substituent selected from the group consisting of fluoro, alkyl, cycloalkyl, alkoxy, aryloxy, amino, silyl, aryl, heteroaryl, thio, and combinations thereof;

[0104] Each R 3 , R 4 , R 5 , R α , R β , R A and R B is independently hydrogen or a substituent selected from the group consisting of the more preferred general substituents defined herein.

[0105] In some embodiments, each R 1 and R 2 is independently a substituent selected from the group consisting of fluoro, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof;

[0106] Each R 3 , R 4 , R 5 , R α , R β , R A and R B is independently hydrogen or a substituent selected from the group consisting of the most preferred general substituents defined herein.

[0107] In some embodiments, X 1 To X 7 Each of is C. In some embodiments, X 1 To X 7 At least one of them is N.

[0108] In some embodiments, X 1 To X 3 Each of them is C.

[0109] In some embodiments, X 1 To X 3 At least one of is N. In some embodiments, X 1 To X 3 Exactly one of is N. In some embodiments, X 1 is N. In some embodiments, X 2 is N. In some embodiments, X 3 It is N.

[0110] In some embodiments, X4 To X 7 Each of them is C.

[0111] In some embodiments, X 4 To X 7 At least one of is N. In some embodiments, X 4 To X 7 Exactly one of is N. In some embodiments, X 4 is N. In some embodiments, X 5 is N. In some embodiments, X 6 is N. In some embodiments, X 7 It is N.

[0112] In some embodiments, K 1 It is a direct key.

[0113] In some embodiments, K 1 Selected from the group consisting of O and S. In some embodiments, K 1 is O. In some embodiments, K 1 It’s S.

[0114] In some embodiments, K 1 Select from N(R α )、P(R α ) and B(R α ). In some embodiments, K 1 Select from C(R α )(R β ) and Si(R α )(R β )

[0115] In some embodiments, M is Ir. In some embodiments, M is Pt or Pd. In some embodiments, M is Pt. In some embodiments, M is Pd.

[0116] In some embodiments, R 1 Contains aryl groups.

[0117] In some embodiments, R 1 A ring system comprising a cyclic portion Q1 fused to an aromatic group. In some embodiments, the ring system comprising the cyclic portion Q1 is directly bonded to the ring A1. In some embodiments, the ring system comprising the cyclic portion Q1 is not directly bonded to the ring A1.

[0118] In some embodiments, the bridging portion of the cyclic moiety Q1 is saturated. In other words, the ring atoms in the cyclic moiety Q1 that are not shared with the aryl group are saturated.

[0119] In some embodiments, the cyclic moiety Q1 is an aromatic ring or an aromatic fused ring system. 1 The moiety comprising is selected from the group consisting of naphthalene, quinoline, isoquinoline, quinazoline, benzofuran, aza-benzofuran, benzoxazole, aza-benzoxazole, benzothiophene, aza-benzothiophene, benzothiazole, aza-benzothiazole, benzoselenophene, aza-benzoselenophene, indene, aza-indene, indole, aza-indole, benzimidazole, aza-benzimidazole, carbazole, aza-carbazole, dibenzofuran, aza-dibenzofuran, dibenzothiophene, aza-dibenzothiophene, quinoxaline, phthalazine, phenanthrene, azaphenanthrene, anthracene, azaanthracene, phenanthridine, fluorene and azafluorene.

[0120] In some embodiments, the cyclic moiety Q1 is further substituted.

[0121] In some embodiments, R 2 A ring system comprising a cyclic portion Q2 containing an aromatic group and fused to the aromatic group. In some embodiments, the ring system comprising the cyclic portion Q2 is directly bonded to the ring A2. In some embodiments, the ring system comprising the cyclic portion Q2 is not directly bonded to the ring A2.

[0122] In some embodiments, the bridging portion of the annular portion Q2 is saturated.

[0123] In some embodiments, the cyclic moiety Q2 is an aromatic ring or an aromatic fused ring system. 2 The moiety comprising is selected from the group consisting of naphthalene, quinoline, isoquinoline, quinazoline, benzofuran, aza-benzofuran, benzoxazole, aza-benzoxazole, benzothiophene, aza-benzothiophene, benzothiazole, aza-benzothiazole, benzoselenophene, aza-benzoselenophene, indene, aza-indene, indole, aza-indole, benzimidazole, aza-benzimidazole, carbazole, aza-carbazole, dibenzofuran, aza-dibenzofuran, dibenzothiophene, aza-dibenzothiophene, quinoxaline, phthalazine, phenanthrene, azaphenanthrene, anthracene, azaanthracene, phenanthridine, fluorene and azafluorene.

[0124] In some embodiments, the cyclic moiety Q2 is further substituted.

[0125] In some embodiments, the compound comprises an electron withdrawing group. In some embodiments, the electron withdrawing group has a Hammett constant greater than 0. In some embodiments, the Hammett constant of the electron withdrawing group is equal to or greater than 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, or 1.1.

[0126] In some embodiments, the compound comprises an electron withdrawing group selected from the group consisting of the following EWG1 list: F, CF3, CN, COCH3, CHO, COCF3, COOMe, COOCF3, NO2, SF3, SiF3, PF4, SF5, OCF3, SCF3, SeCF3, SOCF3, SeOCF3, SO2F, SO2CF3, SeO2CF3, OSeO2CF3, OCN, SCN, SeCN, NC, + N(R k2 )3、(R k2 )2CCN、(R k2 )2CCF3, CNC(CF3)2, BR k3 R k2 , substituted or unsubstituted dibenzoborole, 1-substituted carbazole, 1,9-substituted carbazole, substituted or unsubstituted carbazole, substituted or unsubstituted pyridine, substituted or unsubstituted pyrimidine, substituted or unsubstituted pyrazine, substituted or unsubstituted pyridoxine, substituted or unsubstituted triazine, substituted or unsubstituted oxazole, substituted or unsubstituted benzoxazole, substituted or unsubstituted thiazole, substituted or unsubstituted benzothiazole, substituted or unsubstituted imidazole, substituted or unsubstituted benzimidazole, ketone, carboxylic acid, ester, nitrile, isonitrile, sulfinyl, sulfonyl, partially and fully fluorinated alkyl, partially and fully fluorinated aryl, partially and fully fluorinated heteroaryl, alkyl containing a cyano group, aryl containing a cyano group, heteroaryl containing a cyano group, isocyanate,

[0127]

[0128] Among them, each R k1 Indicates single substitution to the maximum number of substitutions allowed, or no substitution;

[0129] 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

[0130] Where R k1 , R k2 , R k3, R e and R f Each of wherein is independently hydrogen or a substituent selected from the group consisting of general substituents as defined herein.

[0131] In some embodiments, the compound comprises an electron withdrawing group selected from the group consisting of the structures in the following EWG2 checklist:

[0132]

[0133]

[0134] In some embodiments, the compound comprises an electron withdrawing group selected from the group consisting of the structures in the following EWG3 checklist:

[0135] In some embodiments, the compound comprises an electron withdrawing group selected from the group consisting of the structures in the following EWG4 checklist:

[0136] In some embodiments, the compound comprises an electron withdrawing group, which is an electron withdrawing group lacking π electrons. In some embodiments, the electron withdrawing group lacking π electrons is selected from the group consisting of structures in the following Pi-EWG list: CN, COCH3, CHO, COCF3, COOMe, COOCF3, NO2, SF3, SiF3, PF4, SF5, OCF3, SCF3, SeCF3, SOCF3, SeOCF3, SO2F, SO2CF3, SeO2CF3, OSeO2CF3, OCN, SCN, SeCN, NC, + N(R k2 )3. BR k2 R k3, substituted or unsubstituted 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,

[0137]

[0138] where the variables are the same as defined previously.

[0139] In some embodiments, R A , R B , R 1 or R 2 At least one of is an electron withdrawing group in the EWG1 list as defined herein. A , R B , R 1 or R 2 At least one of is an electron withdrawing group in the EWG2 list as defined herein. A , R B , R 1 or R 2 At least one of is an electron withdrawing group in the EWG3 list as defined herein. A , R B , R 1 or R 2 At least one of is an electron withdrawing group in the EWG4 list as defined herein. A , R B , R 1 or R 2 At least one of the groups is an electron withdrawing group in the Pi-EWG list as defined herein.

[0140] In some embodiments, at least one R A comprises an electron withdrawing group from the EWG1 list defined herein. In some embodiments, at least one R Acomprises an electron withdrawing group from the EWG2 list defined herein. In some embodiments, at least one R A comprises an electron withdrawing group from the EWG3 list defined herein. In some embodiments, at least one R A comprises an electron withdrawing group from the EWG4 list defined herein. In some embodiments, at least one R A Contains electron withdrawing groups from the Pi-EWG list as defined herein.

[0141] In some embodiments, at least one R B comprises an electron withdrawing group from the EWG1 list defined herein. In some embodiments, at least one R B comprises an electron withdrawing group from the EWG2 list defined herein. In some embodiments, at least one R B comprises an electron withdrawing group from the EWG3 list defined herein. In some embodiments, at least one R B comprises an electron withdrawing group from the EWG4 list defined herein. In some embodiments, at least one R B Contains electron withdrawing groups from the Pi-EWG list as defined herein.

[0142] In some embodiments, R 1 comprises an electron withdrawing group from the EWG1 list defined herein. In some embodiments, R 1 comprises an electron withdrawing group from the EWG2 list defined herein. In some embodiments, R 1 comprises an electron withdrawing group from the EWG3 list defined herein. In some embodiments, R 1 comprises an electron withdrawing group from the EWG4 list defined herein. In some embodiments, at least one R 1 Contains electron withdrawing groups from the Pi-EWG list as defined herein.

[0143] In some embodiments, R 2 comprises an electron withdrawing group from the EWG1 list defined herein. In some embodiments, R 2 comprises an electron withdrawing group from the EWG2 list defined herein. In some embodiments, R 2 comprises an electron withdrawing group from the EWG3 list defined herein. In some embodiments, R 2 comprises an electron withdrawing group from the EWG4 list defined herein. In some embodiments, R 2 Contains electron withdrawing groups from the Pi-EWG list as defined herein.

[0144] In some embodiments, at least one R Ais not hydrogen. In some embodiments, at least one R A Selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, partially or fully deuterated versions thereof, and combinations thereof.

[0145] In some embodiments, at least one R A Contains aryl or heteroaryl groups.

[0146] In some embodiments, R 1 is a substituted or unsubstituted aryl group.

[0147] In some embodiments, R 2 Having the structure of formula II:

[0148] In some embodiments, R 3 and R 4 different.

[0149] In some embodiments, R 4 It's hydrogen.

[0150] In some embodiments, R 3 is not hydrogen. In some embodiments, R 3 is selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, partially and fully deuterated versions thereof, and combinations thereof. 3 is aryl or partially or fully deuterated aryl. In some embodiments, R 3 is phenyl or a partially or fully deuterated phenyl.

[0151] In some embodiments, R 3 With R C In some embodiments, R 3 With R C are joined or fused to form a 5-membered ring. 3 With R C are joined or fused to form a 6-membered ring. 3 With R C joined or fused to form a ring comprising at least 7 members.

[0152] In some embodiments, R 4 Not hydrogen.

[0153] In some embodiments, R 4 is selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, partially and fully deuterated versions thereof, and combinations thereof. 4 is aryl or partially or fully deuterated aryl. In some embodiments, R 4is phenyl or a partially or fully deuterated phenyl.

[0154] In some embodiments, R 5 Not hydrogen.

[0155] In some embodiments, R 5 Selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, partially and fully deuterated versions thereof, and combinations thereof.

[0156] In some embodiments, R 5 With R C In some embodiments, R 5 With R C are joined or fused to form a 5-membered ring. 5 With R C are joined or fused to form a 6-membered ring. 5 With R C joined or fused to form a ring comprising at least 7 members.

[0157] In some embodiments, R 3 is phenyl or d 5 -phenyl.

[0158] In some embodiments, R 3 and R 4 In some embodiments, R 3 and R 4 different.

[0159] In some embodiments, R 1 It is an alkyl group.

[0160] In some embodiments, R 2 Having the structure of formula II:

[0161] In which R 2 In some embodiments having the structure of Formula II, R 3 is not hydrogen or 3,5-di-tert-butylphenyl, and R 3 With R 4 different.

[0162] In which R 2 In some embodiments having the structure of Formula II, R 5 Not hydrogen.

[0163] In which R 2 In some embodiments having the structure of Formula II, R 5 Selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, partially and fully deuterated versions thereof, and combinations thereof.

[0164] In which R 2 In some embodiments having the structure of Formula II, R 5 With R C In some such embodiments, R 5 With R C are joined or fused to form a 5-membered ring. In some such embodiments, R 5 With R C joined or fused to form a 6-membered ring.

[0165] In some embodiments, R 1 and R 2 fused together to form ring 12. In some embodiments, ring 12 is a 5-membered ring. In some embodiments, ring 12 is a 6-membered ring. In some embodiments, ring 12 comprises 7 or more members.

[0166] In some embodiments, the bridging portion of loop 12 is saturated.

[0167] In some embodiments, ring 12 is an aromatic ring.

[0168] In some embodiments, ring 12 is substituted.

[0169] In some embodiments, R 1 has an atomic mass greater than 78. In some embodiments, R 1 has an atomic mass greater than 156. In some embodiments, R 1 Has an atomic mass greater than 234.

[0170] In some embodiments, R 1 Contains aryl or heteroaryl moieties.

[0171] In some embodiments, R 2 has an atomic mass greater than 78. In some embodiments, R 2 has an atomic mass greater than 156. In some embodiments, R 2 Has an atomic mass greater than 234.

[0172] In some embodiments, R 1 and R 2 In certain embodiments, R 1 and R 2 different.

[0173] In some embodiments, R 1 Not alkyl or substituted or unsubstituted aryl.

[0174] In some embodiments, at least one R B Not hydrogen.

[0175] In some embodiments, at least one R B Contains at least three C atoms. In some embodiments, at least one R B Contains at least four C atoms. In some embodiments, at least one R B Contains at least five C atoms. In some embodiments, at least one R B Contains at least six C atoms.

[0176] In some embodiments, with X 5 Bonded R B Not hydrogen.

[0177] In some embodiments, with X 5 Bonded R B Contains at least three C atoms. In some embodiments, 5 Bonded R B Contains at least four C atoms. In some embodiments, 5 Bonded R B Contains at least five C atoms. In some embodiments, 5 Bonded R B Contains at least six C atoms.

[0178] In some embodiments, the ligand L A Select from the group consisting of the structures in Listing 1 below:

[0179]

[0180]

[0181] Where R AA and R D Each of the above independently represents a single substitution to the maximum number of substitutions allowed, or no substitution;

[0182] Each R AA , R A1 , R A2 , R A3 and R D is independently hydrogen or a substituent selected from the group consisting of general substituents defined herein; and

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

[0184] In L A In some embodiments having the structure of Listing 1, R 3 , R 4 , R 5 , R A , R AA , RA1 , R A2 , R A3 , R B , R C and R D In some such embodiments, at least one R A Partially or completely deuterated. In some embodiments, at least one R AA In some such embodiments, at least one R B In some such embodiments, at least one R C In some such embodiments, at least one R D In some such embodiments, at least R 3 In some such embodiments, at least R 4 In some such embodiments, at least R 5 In some such embodiments, at least R A1 In some such embodiments, at least R A2 In some such embodiments, at least R A3 Partially or fully deuterated.

[0185] In some embodiments of the structure in Listing 1, R A , R AA , R B , R C or R D At least one of comprises / is an electron withdrawing group as defined herein in List EWG 1. In some embodiments, R A , R AA , R B , R C or R D At least one of comprises / is an electron withdrawing group as defined herein in List EWG 2. In some embodiments, R A , R AA , R B , R C or R D At least one of comprises / is an electron withdrawing group as defined herein in List EWG 3. In some embodiments, R A , R AA , R B , R C or R D At least one of comprises / is an electron withdrawing group as defined herein in List EWG 4. In some embodiments, R A , RAA , R B , R C or R D At least one of comprises / is an electron withdrawing group in the list Pi-EWG defined herein.

[0186] In some embodiments of the structure of Listing 1, at least one R A comprises / is an electron withdrawing group as defined herein in List EWG 1. In some embodiments, at least one R A comprises / is an electron withdrawing group as defined herein in List EWG 2. In some embodiments, at least one R A comprises / is an electron withdrawing group as defined herein in List EWG 3. In some embodiments, at least one R A comprises / is an electron withdrawing group as defined herein in List EWG 4. In some embodiments, at least one R A Contains / is an electron withdrawing group in the list Pi-EWG as defined herein.

[0187] In some embodiments of the structure of Listing 1, at least one R AA comprises / is an electron withdrawing group as defined herein in List EWG 1. In some embodiments, at least one R AA comprises / is an electron withdrawing group as defined herein in List EWG 2. In some embodiments, at least one R AA comprises / is an electron withdrawing group as defined herein in List EWG 3. In some embodiments, at least one R AA comprises / is an electron withdrawing group as defined herein in List EWG 4. In some embodiments, at least one R AA Contains / is an electron withdrawing group in the list Pi-EWG as defined herein.

[0188] In some embodiments of the structure of Listing 1, at least one R B comprises / is an electron withdrawing group as defined herein in List EWG 1. In some embodiments, at least one R B comprises / is an electron withdrawing group as defined herein in List EWG 2. In some embodiments, at least one R B comprises / is an electron withdrawing group as defined herein in List EWG 3. In some embodiments, at least one R B comprises / is an electron withdrawing group as defined herein in List EWG 4. In some embodiments, at least one R B Contains / is an electron withdrawing group in the list Pi-EWG as defined herein.

[0189] In some embodiments of the structure of Listing 1, at least one R C comprises / is an electron withdrawing group as defined herein in List EWG 1. In some embodiments, at least one R C comprises / is an electron withdrawing group as defined herein in List EWG 2. In some embodiments, at least one R C comprises / is an electron withdrawing group as defined herein in List EWG 3. In some embodiments, at least one R C comprises / is an electron withdrawing group as defined herein in List EWG 4. In some embodiments, at least one R C Contains / is an electron withdrawing group in the list Pi-EWG as defined herein.

[0190] In some embodiments of the structure of Listing 1, at least one R D comprises / is an electron withdrawing group as defined herein in List EWG 1. In some embodiments, at least one R D comprises / is an electron withdrawing group as defined herein in List EWG 2. In some embodiments, at least one R D comprises / is an electron withdrawing group as defined herein in List EWG 3. In some embodiments, at least one R D comprises / is an electron withdrawing group as defined herein in List EWG 4. In some embodiments, at least one R D Contains / is an electron withdrawing group in the list Pi-EWG as defined herein.

[0191] In some embodiments, R 3 , R 4 , R 5 , R A , R AA , R A1 , R A2 , R A3 , R B , R C and R D Each of is independently selected from the list consisting of the structures in List S below:

[0192]

[0193]

[0194]

[0195]

[0196]

[0197]

[0198]

[0199]

[0200]

[0201]

[0202]

[0203]

[0204] In some embodiments, the ligand L A Choose from L Ai -(Ri')(Rj')(Rk')(Rl'), wherein i is an integer from 1 to 19, and each of i', j', k' and l' is independently an integer from 1 to 135, except that: when i is 1, 2 or 3, i' and k' are different, and / or j' is not 1; wherein, when i is 1, 2 or 3, if i'=27 or 28, i' and k' are different; wherein, when i is 8, 9 or 10, l' is not 1; wherein, when i is 11, i' is not 1 or 41, and i' and k' are different, or j' is not 1; and L A1 -(R1)(R1)(R1)(R1) to L A19 - Each of (R135)(R135)(R135)(R135) is defined in Listing 2 below:

[0205]

[0206]

[0207]

[0208] and

[0209] Where R1 to R135 have the structure defined in Listing 3 below:

[0210]

[0211]

[0212]

[0213]

[0214]

[0215]

[0216] In some embodiments, the compound has the formula M(L A ) p (L B ) q (L C ) r , where L B and L C Each is a bidentate ligand; and wherein p is 1, 2 or 3; q is 0, 1 or 2; r is 0, 1 or 2; and p+q+r is the oxidation state of the metal M.

[0217] In some embodiments, the compound has a formula selected from the group consisting of: Ir(L A )3、Ir(L A )(L B )2、Ir(L A )2(L B )、Ir(L A )2(L C ) and Ir(L A )(L B )(L C ); and where L A , L B and L C Different from each other.

[0218] In some embodiments, L B is a substituted or unsubstituted phenylpyridine, and L C It is a substituted or unsubstituted acetylacetonate.

[0219] In some embodiments, the compound may have the formula Pt(L A )(L B ); and where L A and L B Can be the same or different. In some embodiments, L A and L B connected to form a tetradentate ligand.

[0220] In some embodiments, the ligand L B Contains an electron withdrawing group from the EWG1 list defined herein. In some embodiments, the ligand L B Contains an electron withdrawing group from the EWG2 list defined herein. In some embodiments, the ligand L B Contains an electron withdrawing group from the EWG3 list defined herein. In some embodiments, the ligand L B Contains an electron withdrawing group from the EWG4 list defined herein. In some embodiments, the ligand LB Contains electron withdrawing groups from the Pi-EWG list as defined herein.

[0221] In some embodiments, the ligand L C Contains an electron withdrawing group from the EWG1 list defined herein. In some embodiments, the ligand L C Contains an electron withdrawing group from the EWG2 list defined herein. In some embodiments, the ligand L C Contains an electron withdrawing group from the EWG3 list defined herein. In some embodiments, the ligand L C Contains an electron withdrawing group from the EWG4 list defined herein. In some embodiments, the ligand L C Contains electron withdrawing groups from the Pi-EWG list as defined herein.

[0222] In some embodiments, L B and L C Each is independently selected from the group consisting of the structures defined in Listing 4 below:

[0223]

[0224]

[0225]

[0226] in:

[0227] T is selected from the group consisting of B, Al, Ga and In;

[0228] 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 ;

[0229] Y 1 To Y 13 Each of which is independently selected from the group consisting of C and N;

[0230] Y'Select from the group consisting of: BR e , BR e R f NR e , PR e 、P(O)R e ,O,S,Se,C=O,C=S,C=Se,C=NR e 、C=CRe R f 、S=O、SO2、CR e R f 、SiR e R f and GeR e R f ;

[0231] R e With R f may be fused or joined to form a ring;

[0232] Each R a , R b , R c and R d independently represent mono-substitution to the maximum allowed number of substitutions, or no substitution;

[0233] R a1 , R b1 , R c1 , R d1 , R a , R b , R c , R d , R e and R f Each of is independently hydrogen or a substituent selected from the group consisting of general substituents defined herein; and

[0234] 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.

[0235] In some embodiments, L B and L C Each independently selected from the group consisting of the structures in Listing 5 below:

[0236]

[0237]

[0238]

[0239]

[0240]

[0241]

[0242]

[0243] in:

[0244] R a '、R b '、R c '、R d ' and R e 'Each independently represents zero substitution, single substitution or up to the maximum allowed number of substitutions on the rings to which it is connected;

[0245] R a '、R b '、R c '、R d ' and R e ' are each independently hydrogen or a substituent selected from the group consisting of general substituents defined herein; and

[0246] R a '、R b '、R c '、R d ' and R e The two substituents in ' may be fused or joined to form a ring or to form a multidentate ligand.

[0247] In some embodiments, L B Include wherein the variables are the same as previously defined. In some embodiments, Y 1 To Y 4 In some embodiments, Y 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 group, a silane group or a germanium 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 group, a silane group or a germanium group. 1 To Y 3 It's C, Y 4 is N, and with Y3 Connected R a is a tertiary alkyl group, a silane group or a germanium group. 1 To Y 3 It's C, Y 4 is N, and with Y 2 Connected R a is a tertiary alkyl group, a silane group or a germanium group. In some embodiments, at least one R b is a tertiary alkyl, a silane group or a germanium 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.

[0248] In some embodiments, the compound has the formula Ir(L A )3, Formula Ir(L A )(L Bk )2, Formula Ir(L A )2(L Bk ), formula Ir(L A )2(L Cj-I ) or formula Ir(L A )2(L Cj-II ),

[0249] Where L A According to any embodiment described herein, including L A1 -(R1)(R1)(R1)(R1) to L A19 -(R135)(R135)(R135)(R135);

[0250] Where k is an integer from 1 to 522, and each L Bk With the following structure defined in Listing 6:

[0251]

[0252]

[0253]

[0254]

[0255]

[0256]

[0257]

[0258]

[0259]

[0260]

[0261]

[0262]

[0263]

[0264] Among them, each L Cj-I Has a structure based on the following formula: and

[0265] Each L Cj-II Has a structure based on the following formula: For L Cj-I and L Cj-II Each L in Cj For example, R 201 and R 202 Each is independently defined in Listing 7 below:

[0266]

[0267]

[0268]

[0269]

[0270]

[0271]

[0272]

[0273]

[0274]

[0275]

[0276]

[0277]

[0278] Where R D1 To R D246 With the following structure defined in Listing 8:

[0279]

[0280]

[0281]

[0282] In some embodiments, the compound is selected from the group consisting of Bk The group consisting of only those compounds corresponding to one of the following: L B1 , L B2 , L B18 , L B28 , L B38 , L B108 , L B118 , L B122 , L B124 , L B126 , L B128 , L B130 , L B132 , L B134 , L B136 , L B138 , L B140 , L B142 , L B144 , L B156 , L B158 , L B160 , L B162 , L B164 , L B168 , L B172 , L B175 , L B204 , L B206 , L B214 , L B216 , L B218 , L B220 , L B222 , L B231 , L B233 , L B235 , L B237 , L B240 , L B242 , L B244 , L B246 , L B248 , L B250 , L B252 , L B254 , L B256 , L B258 , L B260 , L B262 , L B264 , L B265 , L B266, L B267 , L B268 , L B269 and L B270 .

[0283] In some embodiments, the compound is selected from the group consisting of Bk The group consisting of only those compounds corresponding to one of the following: L B1 , L B2 , L B18 , L B28 , L B38 , L B108 , L B118 , L B122 , L B126 , L B128 , L B132 , L B136 , L B138 , L B142 , L B156 , L B162 , L B204 , L B206 , L B214 , L B216 , L B218 , L B220 , L B231 , L B233 , L B 237 , L B 264 , L B265 , L B266 , L B267 , L B268 , L B269 and L B270 .

[0284] In some embodiments, the compound is selected from the group consisting of Cj-I or L Cj-II The group consisting of only those compounds of the ligands whose corresponding 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 , RD49 , 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 .

[0285] In some embodiments, the compound is selected from the group consisting of Cj-I or L Cj-II The group consisting of only those compounds of the ligands whose corresponding R 201 and R 202 is defined as one selected from the following structures: R D1 , R D3 , R D4 , R D5 , R D9 , R D10 , RD17 , 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 .

[0286] In some embodiments, the compound is selected from L Cj-I The group consisting of only those compounds whose ligand has one of the structures in List 9 below:

[0287]

[0288] In some embodiments, L A is selected from the group consisting of the structures in Listing 1 and Listing 2, and L B Selected from the group consisting of the structures in Listing 4, Listing 5, and Listing 6. In some embodiments, L A is selected from the group consisting of the structures in Listing 1, and L B Selected from the group consisting of the structures in Listing 6. In some embodiments, L A Selected from L defined in this article A 1-(R1)(R1)(R1)(R1) to L A19-(R135)(R135)(R135)(R135) composed of L Ai -(Ri')(Rj')(Rk')(Rl') group list 2, wherein i is an integer from 1 to 19, and L B Choose from L Bk A group consisting of the structures in Listing 6, where k is an integer from 1 to 522.

[0289] In some embodiments, the compound may be Ir(L A )2(L B )、Ir(L A )(L B )2 or Ir(L A )(L B )(L C ). In some of these embodiments, L A Can have Formula I as defined herein. In some of these embodiments, L A can be selected from the group consisting of the structures in Listing 1 and Listing 2 as defined herein. In some of these embodiments, L B Can be selected from the group consisting of the structures in List 4, List 5 and List 6 as defined herein. In some of these embodiments, the compound can be Ir(L Ai -(Ri')(Rj')(Rk')(Rl'))2(L B )、Ir(L Ai -(Ri')(Rj')(Rk')(Rl'))(L B )2、Ir(L A )2(L Bk ),Ir(L A )(L Bk )2、Ir(L Ai -(Ri')(Rj')(Rk')(Rl'))2(L Bk )、Ir(L Ai -(Ri')(Rj')(Rk')(Rl'))(L Bk )2、Ir(L Ai -(Ri')(Rj')(Rk')(Rl'))(L Bk )(L Cj-I ) or Ir(L Ai -(Ri')(Rj')(Rk')(Rl'))(L B )(L Cj-II ).

[0290] In some embodiments, the compound is selected from the group consisting of the structures in Listing 10 below:

[0291]

[0292]

[0293] In some embodiments, the compound has Formula III:

[0294]

[0295] in:

[0296] M 1 is Pd or Pt;

[0297] Moieties E and F are each independently a monocyclic or polycyclic ring structure comprising a 5-membered and / or 6-membered carbocyclic or heterocyclic ring;

[0298] Z 1 and Z 2 each independently is C or N;

[0299] K 1 ' and K 2 ' are independently selected from the group consisting of direct bonds, O and S, wherein K 1 , K 1 ' and K 2 At least two of ' are direct keys;

[0300] L 1 and L 2 Each is independently selected from the group consisting of a direct bond, BR, BRR', NR, PR, P(O)R, O, S, Se, C=O, C=S, C=Se, C=NR, C=CRR', S=O, SO2, CR, CRR', SiRR', GeRR', alkylene, cycloalkyl, aryl, cycloalkylene, arylene, heteroarylene, and combinations thereof;

[0301] R E and R F Each independently represents zero substitution, monosubstitution or up to the maximum allowed number of substitutions on the ring to which it is connected;

[0302] R, R', R E and R F Each of is independently hydrogen or a substituent selected from the group consisting of general substituents defined herein; and

[0303] When chemically feasible, two adjacent R A , R B , R C , R E and R F They may be joined or fused together to form a ring.

[0304] In some embodiments of Formula III, each R 3 , R 4 , R 5 , R α , R β , R A , R B , R E and R F are independently hydrogen or a substituent selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silanyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thio, and combinations thereof.

[0305] In some embodiments of Formula III, R, R', R 1 , R 2 , 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 At least one of R or R' is partially or fully deuterated. In some embodiments, at least one of R or R' is partially or fully deuterated.

[0306] In some embodiments of Formula III, at least one R A is or comprises an electron withdrawing group as defined in EWG1. A is or comprises an electron withdrawing group in the EWG2 list as defined herein. In some embodiments, at least one R A is or comprises an electron withdrawing group in the EWG3 list as defined herein. In some embodiments, at least one R A is or comprises an electron withdrawing group in the EWG4 list as defined herein. In some embodiments, at least one R A is or comprises an electron withdrawing group in the Pi-EWG list as defined herein.

[0307] In some embodiments of Formula III, at least one R B is or comprises an electron withdrawing group as defined in EWG1. B is or comprises an electron withdrawing group in the EWG2 list as defined herein. In some embodiments, at least one RB is or comprises an electron withdrawing group in the EWG3 list as defined herein. In some embodiments, at least one R B is or comprises an electron withdrawing group in the EWG4 list as defined herein. In some embodiments, at least one R B is or comprises an electron withdrawing group in the Pi-EWG list as defined herein.

[0308] In some embodiments of Formula III, at least one R E is or comprises an electron withdrawing group as defined in EWG1. E is or comprises an electron withdrawing group in the EWG2 list as defined herein. In some embodiments, at least one R E is or comprises an electron withdrawing group in the EWG3 list as defined herein. In some embodiments, at least one R E is or comprises an electron withdrawing group in the EWG4 list as defined herein. In some embodiments, at least one R E is or comprises an electron withdrawing group in the Pi-EWG list as defined herein.

[0309] In some embodiments of the structure of Formula III, at least one R F is or comprises an electron withdrawing group as defined in EWG1. F is or comprises an electron withdrawing group in the EWG2 list as defined herein. In some embodiments, at least one R F is or comprises an electron withdrawing group in the EWG3 list as defined herein. In some embodiments, at least one R F is or comprises an electron withdrawing group in the EWG4 list as defined herein. In some embodiments, at least one R F is or comprises an electron withdrawing group in the Pi-EWG list as defined herein.

[0310] In some embodiments, Formula III comprises an electron withdrawing group from the EWG1 list as defined herein. In some embodiments, Formula III comprises an electron withdrawing group from the EWG2 list as defined herein. In some embodiments, Formula III comprises an electron withdrawing group from the EWG3 list as defined herein. In some embodiments, Formula III comprises an electron withdrawing group from the EWG4 list as defined herein. In some embodiments, Formula III comprises an electron withdrawing group from the Pi-EWG list as defined herein.

[0311] In some embodiments of Formula III, both moiety E and moiety F are 6-membered aromatic rings. In some embodiments of Formula III, moiety F is a 5-membered or 6-membered heteroaromatic ring.

[0312] In some embodiments of Formula III, L 1 It is O or CRR'.

[0313] In some embodiments of Formula III, Z 2 is N and Z 1 is C. In some embodiments of Formula III, Z 2 is C and Z 1 It is N.

[0314] In some embodiments of Formula III, L 2 is a direct bond. In some embodiments of Formula III, L 2 It is NR.

[0315] In some embodiments of Formula III, K 1 , K 1 ' and K 2 ' are all direct bonds. In some embodiments of Formula III, K 1 , K 1 ' and K 2 One of the ' is O.

[0316] In some embodiments, the compound may have Formula XA:

[0317] Or XB:

[0318] Where X 30 To X 32 each independently is C or N;

[0319] R E ' indicates single substitution to the maximum number of substitutions allowed, or no substitution;

[0320] R E '、R EE0 , R EE1 and R EE2 Each of is independently hydrogen or a substituent selected from the group consisting of general substituents defined herein; and

[0321] Any two substituents may be joined or fused to form a ring.

[0322] In some embodiments of Formula XA or Formula XB, R E 'Not with R EE1 or R EE2 joined or fused to form a ring.

[0323] In some embodiments of Formula XA or Formula XB, R EE0is selected from the group consisting of 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, selenoalkyl, and combinations thereof. In some embodiments, R EE0 is not H or D. In some embodiments, R EE0 is alkyl, cycloalkyl, aryl or heteroaryl. In some embodiments, R EE0 It is C6H5, C6D5, C(CH3)3, C(CD3)3, CD2C(CH3)3, CH3, CD3, cyclopentyl, cyclohexyl or neopentyl.

[0324] In some embodiments of Formula XA or Formula XB, X 30 To X 32 Each is C. In some embodiments, X 30 To X 32 One of is N. In some embodiments, X 30 and X 32 One of is N. In some embodiments, X 31 It is N.

[0325] In some embodiments of Formula XA or Formula XB, R EE1 With R EE2 In some embodiments, R EE1 Different from R EE2 .

[0326] In some embodiments of Formula XA or Formula XB, R EE1 and R EE2 At least one of the R comprises a chemical group containing at least three 6-membered aromatic rings, wherein adjacent aromatic rings are not fused to each other. EE1 or R EE2 At least one of the R comprises a chemical group containing at least four 6-membered aromatic rings, wherein adjacent aromatic rings are not fused. EE1 or R EE2 At least one of the R comprises a chemical group containing at least five 6-membered aromatic rings, wherein adjacent aromatic rings are not fused. EE1 or R EE2 At least one of the R comprises a chemical group containing at least six 6-membered aromatic rings, wherein adjacent aromatic rings are not fused. EE1 and R EE2 Each of the above independently comprises a chemical group comprising at least three to six 6-membered aromatic rings, wherein adjacent aromatic rings are not fused to each other.

[0327] In some embodiments of Formula XA or Formula XB, R EE1 or R EE2 At least one of the groups contains a group R W , where R W Having a structure selected from the group consisting of: Formula XIIIA, ---Q A (R 1a )(R 2a ) a (R 3a ) b , Formula XIIIB Japanese style XIIIC in:

[0328] X 130 To X 138 Each of is independently C or N;

[0329] Y S , Y T and Y U each of which is independently CRR', SiRR' or GeRR';

[0330] n is an integer from 1 to 8,

[0331] When n is greater than 1, each Y S Can be the same or different;

[0332] Q A Selected from the group consisting of: C, Si, Ge, N, P, O, S, Se and B;

[0333] Each of a and b is independently 0 or 1;

[0334] If Q A If it is C, Si or Ge, then a+b=2;

[0335] If Q A If it is N or P, then a+b=1;

[0336] If Q A is B, then a+b can be 1 or 2;

[0337] If Q A If it is O, S or Se, then a+b=0;

[0338] R SS , R TT and R UU Each of the above independently represents a single substitution to the maximum permissible number of substitutions, or no substitution;

[0339] Each R, R', R1a , R 2a , R 3a , R SS , R TT and R UU is independently hydrogen or a substituent selected from the group consisting of general substituents defined herein; and

[0340] Any two substituents may be optionally fused or joined to form a ring.

[0341] In some embodiments, at least one Y S , Y T or Y U is SiRR' or GeRR'. In some embodiments, each Y S , Y T and Y U It's CRR'.

[0342] In some embodiments of Formula XA or Formula XB, R EE1 and R EE2 At least one of the groups contains a group R W In some embodiments, R EE1 and R EE2 Each of the groups R W In some embodiments, R EE1 and R EE2 Each of the formula XIIIA. In some embodiments, R EE1 and R EE2 Each of the formula XIIIB comprises. In some embodiments, R EE1 and R EE2 Each of the formula XIIIC comprises. In some embodiments, R EE1 or R EE2 Containing Formula XIIIA, and R EE1 and R EE2 In another embodiment, R EE1 and R EE2 Any one of the formula XIIIA, and R EE1 and R EE2 In another embodiment, R EE1 or R EE2 Any one of the formula XIIIB, and R EE1 and R EE2 Another of the formulas comprises formula XIIIC.

[0343] In some embodiments of Formula XA or Formula XB, R EE1 has a molecular weight (MW) greater than 15 g / mol, and R EE2With greater than R EE1 In some embodiments, R EE1 has a molecular weight (MW) greater than 56 g / mol, and R EE2 The molecular weight is greater than R EE1 In some embodiments, R EE1 has a molecular weight (MW) greater than 76 g / mol, and R EE2 The molecular weight is greater than R EE1 In some embodiments, R EE1 has a molecular weight (MW) greater than 81 g / mol, and R EE2 The molecular weight is greater than R EE1 In some embodiments, R EE1 or R EE2 has a molecular weight (MW) greater than 165 g / mol. EE1 or R EE2 has a molecular weight (MW) greater than 166 g / mol. In some embodiments, R EE1 or R EE2 Having a molecular weight (MW) greater than 182 g / mol.

[0344] In some embodiments of Formula XA or Formula XB, R EE1 The 6-membered aromatic ring has EE2 In some embodiments, R EE1 The 6-membered aromatic ring has EE2 In some embodiments, R EE1 The 6-membered aromatic ring has EE2 In some embodiments, R EE1 The 6-membered aromatic ring has EE2 In some embodiments, R EE1 The 6-membered aromatic ring has EE2 Five more.

[0345] In some embodiments of Formula XA or Formula XB, R EE1 contains at least one heteroatom and R EE2 In some embodiments, R EE1 Contains at least two heteroatoms and R EE2 In some embodiments, R EE1 Contains at least three heteroatoms and R EE2 In some embodiments, R EE1 Contains exactly one heteroatom and R EE2In some embodiments, R EE1 Contains exactly two heteroatoms and R EE2 In some embodiments, R EE1 contains exactly three heteroatoms and R EE2 In some embodiments, R EE1 contains exactly one heteroatom, and R EE2 Contains exactly one EE1 In some embodiments, R EE1 contains exactly one heteroatom, and R EE2 Contains exactly one EE1 The heteroatoms in are the same heteroatoms.

[0346] In some embodiments of Formula XA or Formula XB, R EE1 Contains exactly two heteroatoms and R EE2 Contains exactly one heteroatom. In some embodiments, R EE1 Contains exactly two heteroatoms and R EE2 Contains exactly two heteroatoms. In some embodiments, R EE1 contains exactly three heteroatoms and R EE2 Contains exactly one heteroatom. In some embodiments, R EE1 contains exactly three heteroatoms and R EE2 Contains exactly two heteroatoms. In some embodiments, R EE1 contains exactly three heteroatoms and R EE2 Contains exactly three heteroatoms.

[0347] In some embodiments of Formula XA or Formula XB, R EE1 and R EE2 At least one of R comprises an aromatic ring fused to a non-aromatic ring. EE1 and R EE2 All include an aromatic ring fused to a non-aromatic ring. In some embodiments, the aromatic ring is a benzene ring and the non-aromatic ring is a cycloalkyl ring.

[0348] In some embodiments of Formula XA or Formula XB, R EE1 and R EE2 At least one of is partially or fully deuterated. In some embodiments, R EE1 and R EE2 All are partially or fully deuterated.

[0349] In some embodiments, the compound is selected from the group consisting of compounds having the formula Pt(L A' The group consisting of compounds of )(Ly):

[0350]

[0351] Where L A' Select from the group consisting of the following structures in Listing 11:

[0352]

[0353]

[0354] Where L y Select from the group consisting of the following structures in Listing 12:

[0355]

[0356]

[0357]

[0358] Where R AA and R D Each of the above independently represents a single substitution to the maximum number of substitutions allowed, or no substitution;

[0359] Among them, each R AA , R D , R X and R Y is independently hydrogen or a substituent selected from the group consisting of general substituents defined herein; and

[0360] Any two substituents therein may be optionally fused or joined to form a ring.

[0361] In some embodiments, R 3 , R 4 , R 5 , R A , R AA , R A1 , R A2 , R A3 , R B , R C , R D , R E , R F , R X and R Y Each of is independently selected from the group consisting of List S defined herein.

[0362] In some embodiments, R A , R B , R C , R E , R F , R AA, R X and R Y At least one of is independently selected from the group consisting of the structures in Listing 13 below:

[0363]

[0364] Where Q A , Q B , Q C , Q D and Q E Each of the above independently represents a single substitution to the maximum number of substitutions allowed, or no substitution;

[0365] Among them, each Q A , Q B , Q C , Q D , Q E , Q A1 , Q B1 , Q C1 , Q D1 and Q E1 are independently hydrogen or a substituent selected from the group consisting of alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boryl, aralkyl, alkoxy, aryloxy, amino, silanyl, germanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thiol, sulfinyl, sulfonyl, phosphino, selenanyl, and combinations thereof;

[0366] Each Y aa and Y bb are independently selected from the group consisting of a direct bond, BR, BRR', NR, PR, O, S, Se, C=O, C=S, C=Se, C=NR, C=CRR', S=O, SO2, CR, CRR', SiRR', GeRR', alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof; and any two substituents may be joined or fused to form a ring; and

[0367] wherein each of R and R' is independently hydrogen or a substituent selected from the group consisting of general substituents defined herein.

[0368] In some embodiments, the compound is selected from the group consisting of compounds having the formula Pt(L A' The group consisting of compounds of )(Ly):

[0369]

[0370] Where L A' Selected from the group consisting of: L A'm-(Rs)(Rt)(Ru)(Rv), wherein m is an integer from 1 to 19, and each of s, t, u and v is independently an integer from 1 to 135, except for the following: wherein, when m is 1, 2 or 3, s and u are different, and / or t is not 1; wherein, when m is 1, 2 or 3, if s=27 or 28, s and u are different; wherein, when m is 8, 9 or 10, v is not 1; wherein, when m is 11, s is not 1 or 41, and s and u are different, or t is not 1; and L A'1 -(R1)(R1)(R1)(R1) to L A'19 -(R135)(R135)(R135)(R135) are each defined in Listing 14 below:

[0371]

[0372]

[0373]

[0374] Where L y Selected from the group consisting of: L y j-(Rs)(Rt)(Ru)(Rv), wherein j is an integer from 1 to 33, wherein each of s, t and u is independently an integer from 1 to 135, and L y 1-(R1)(R1)(R1) to L y Each of 33-(R135)(R135)(R135) is defined in the following Listing 15:

[0375]

[0376]

[0377]

[0378]

[0379] In some embodiments, the compound is selected from the group consisting of the structures in Listing 16 below:

[0380]

[0381]

[0382] wherein Ph represents phenyl.

[0383] In some embodiments, the first ligand L having Formula I described herein 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, the deuterated percentage has its ordinary meaning and includes the percentage of all possible hydrogen atoms (e.g., hydrogen or deuterium positions) occupied by deuterium atoms in the compound. In some embodiments, the carbon atoms included by the ring coordinated to the metal M are completely or partially deuterated. In some embodiments, the carbon atoms included by the polycyclic system coordinated to the metal M are completely or partially deuterated. In some embodiments, the substituents connected to the monocyclic or fused polycyclic system coordinated to the metal M are completely or partially deuterated.

[0384] 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. Narrower FWHM means better color purity for OLED display applications.

[0385] In the above defined 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 ligand L is the farthest from the metal M among all the atoms in B If present, the second substituent R II , where the second substituent R II The first atom a-II in the ligand L B The ligand L is the farthest from the metal M among all the atoms in C If present, a third substituent R III , where the third substituent R III The first atom in a-III is in the ligand L C It is the farthest from the metal M among all the atoms in the atom.

[0386] In this type of heteroleptic compound, the vector V D1 、V D2 and V D3 It can be 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 atom 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 atom a-II in V D3 represents the direction from the metal M to the first atom a-III, and the vector V D3 With a metal M and a third substituent R III The value of the straight-line distance D between the first atom a-III in 3 .

[0387] 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 non-substituents R in the compound. 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 greater than the radius r.

[0388] 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 defined as D1 、V D2 and V D3 At least one angle between the transition dipole moment axis and the vector V is less than 40°. 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 At least two angles between the transition dipole moment axis and the vector V are less than 20°. D1 、V D2 and V D3 At least two of the angles therebetween are smaller than 15° or 10°.

[0389] In some embodiments, the transition dipole moment axis is aligned with the vector V D1 、V D2 and V D3 All three angles between are less than 20°. In some embodiments, the transition dipole moment axis and the vector V D1 、V D2 and V D3 All three angles between are less than 15° or 10°.

[0390] 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.

[0391] 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. Pat. No. 10,672,997, the disclosure of which is incorporated herein by reference in its entirety. In U.S. Pat. No. 10,672,997, the horizontal dipole ratio (HDR) of a compound is discussed, not VDR. However, a person skilled in the art will readily understand that VDR=1-HDR.

[0392] In some embodiments, the compound can be an emitting dopant. In some embodiments, the compound can generate 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 various isomers of individual isomers and 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 other ligands. In some embodiments, each ligand can be different from all other ligands. This is also true in the embodiments where the ligand coordinated to the metal can be connected to other ligands coordinated to the metal to form a tridentate, tetradentate, pentadentate or hexadentate ligand. Thus, where the 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 linking ligands may be different from the other ligand(s).

[0393] In yet 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.

[0394] 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 may be part of a larger chemical structure. Such chemical structures may 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 a compound, but one of the hydrogens has been removed and replaced with a bond to the remainder of the chemical structure. As used herein, a "multivalent variant of a compound" refers to a portion identical to a compound, but more than one hydrogen has been removed and replaced with one or more bonds to the remainder of the chemical structure. In the case of a supramolecule, the compounds of the present invention may also be incorporated into a supramolecular complex 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 may 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 may be a part of structure A, and after it becomes a part of structure A, one or more of the H or D on a given part B structure may be further substituted.

[0395] C. OLEDs and Devices of the Present Disclosure

[0396] In another aspect, the present disclosure also provides an OLED device comprising a first organic layer, wherein the first organic layer contains a compound disclosed in the above compound section of the present disclosure.

[0397] In some embodiments, the OLED comprises: an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises a first ligand L comprising Formula I A of compounds.

[0398] In some embodiments, the organic layer is selected from the group consisting of: HIL, HTL, EBL, EML, HBL, ETL, and EIL. In some embodiments, the organic layer may be an emissive layer and the compound as described herein may be an emissive dopant or a non-emissive dopant.

[0399] In some embodiments, the organic layer may further include a host, wherein the host includes 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, oxaborabine, dihydroacridine, xanthene, dihydrobenzazasilane, dibenzooxasilane, 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-boranaphtho[3,2,1-de]anthracene). In some embodiments, the host can be selected from the group consisting of the following structures in Host Group 1:

[0400]

[0401]

[0402]

[0403]

[0404]

[0405]

[0406]

[0407] in:

[0408] Each of J1 to J6 is independently C or N;

[0409] L' is a direct bond or an organic linking group;

[0410] 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';

[0411] R A' , R B' , R C' , R D' , R E' , R F' and R G' Each of the above independently represents a single substitution up to a maximum number of substitutions, or no substitution;

[0412] Each R, R', R A' , R B' , R C' , R D' , R E' , R F' and R G' are independently hydrogen or a substituent selected from the group consisting of general substituents as defined herein; any two substituents may be joined or fused to form a ring;

[0413] Also, where possible, each unsubstituted aromatic carbon atom is optionally replaced with N to form an aza-substituted ring.

[0414] In some embodiments, at least one of J1 to J3 is N. In some embodiments, at least two of J1 to J3 are N. In some embodiments, all three of J1 to J3 are N. In some embodiments, each Y CC and Y DD are independently O, S or SiRR', or more preferably O or S. In some embodiments, at least one unsubstituted aromatic carbon atom is replaced by N to form a nitrogen heterocycle.

[0415] In some embodiments, the subject is selected from the group consisting of EG1-MG1-EG1 to EG53-MG27-EG53 having the formula EGa-MGb-EGc, or EG1-EG1 to EG53-EG53 having the formula EGa-EGc when MGb is deficient, 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:

[0416]

[0417]

[0418] The structures of MG1 to MG27 are as follows:

[0419]

[0420] 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.

[0421] In some embodiments, the host can be any of its aza-substituted variants, its fully or partially deuterated variants, and combinations thereof. In some embodiments, the host has the formula EGa-MGb-Egc and is selected from the group consisting of h1 to h112 as defined in the following List of Host Group 2, wherein each of MGb, EGa, and EGc is defined as follows:

[0422]

[0423]

[0424] 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 its bonding position in the MGb structure.

[0425] In some embodiments, the organic layer may further include a host, wherein the host includes a metal complex.

[0426] In some embodiments, the emission layer may include two hosts: a first host and a second host. In some embodiments, the first host is a hole transport host and the second host is an electron transport host. In some embodiments, the first host is a hole transport host and the second host is a bipolar host. In some embodiments, the first host is an electron transport host and the second host is a bipolar host. In some embodiments, the first host and the second host may form an exciplex. In some embodiments, the emission 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 transport host and an electron transport host. In some embodiments, the third host forms an exciplex with one of the first host and the second host or with both the first host and the second host. In some embodiments, the emission 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 transport host and an electron transport host. In some embodiments, the fourth host forms an exciplex with one of the first host, the second host and the third host, with two of the first host, the second host and the third host, or with each of the first host, the second host and the third host. In some embodiments, the LUMO of the electron transport subject is less than -2.4eV, less than -2.5eV, less than -2.6eV or less than -2.7eV. In some embodiments, the HOMO of the hole transport subject is higher than -5.6eV, higher than -5.5eV, higher than -5.4eV or higher than -5.35eV. HOMO and LUMO values ​​can be determined using solution electrochemistry. Solution cyclic voltammetry and differential pulse voltammetry can be performed using a CH Instruments model 6201B constant potentiostat, using anhydrous dimethylformamide (DMF) solvent and tetrabutylammonium hexafluorophosphate as a loaded electrolyte. Glassy carbon, platinum wire and silver wire are used as working electrode, counter electrode and reference electrode, respectively. The electrochemical potential can be measured by measuring the peak potential difference using differential pulse voltammetry using an internal ferrocene-ferrocene salt redox pair (Fc / Fc+) as an internal standard.According to the literature ((a) Fink R.; Heischkel Y.; Thelakkat M.; Schmidt H.-W., Chem. Mater. 1998, 10, 3620-3625; (b) Pommerehne J.; Vestweber H.; Guss W.; Mahrt R.F.; Bassler H.; Porsch M.; Daub J.) J.), Journal of Advanced Materials (J. Adv. Mater. 1995, 7, 551), the corresponding highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energies were determined by comparing the cation and anion redox potentials with those of a ferrocene reference (4.8 eV relative to vacuum).

[0427] In some embodiments, the compounds as 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 excited complex 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 one or all of the sensitizer, the acceptor, and the final emitter. In some embodiments, the emission of the acceptor at room temperature has a full width at half maximum (FWHM) equal to or less than 50, 45, 40, 35, 30, 25, 20, 15, 10, or 5 nm. Narrower FWHM means better color purity for OLED display applications.

[0428] As used herein, phosphorescence generally refers to the emission of photons with a change in the electron spin quantum number, 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 excited complex formation involves a triplet emitter, such excited complexes 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. Fluorescent emitters can be delayed fluorescent or non-delayed fluorescent emitters. Depending on the spin state, the 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 fluorescent OLEDs can exceed the 25% spin statistical limit through delayed fluorescence. There are two types of delayed fluorescence, namely P-type and E-type delayed fluorescence. P-type delayed fluorescence is produced by triplet-triplet annihilation (TTA). On the other hand, E-type delayed fluorescence does not rely on the collision of two triplets, but on the thermal population between the triplet and singlet excited states. Thermal energy can activate the triplet state to transfer 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 requires the compound or exciplex 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 ). There are two main types of TADF emitters, one is called donor-acceptor 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 (e.g., an amino or carbazole derivative) and an electron acceptor portion (e.g., an N-containing six-membered aromatic ring or a cyano-substituted aromatic ring). A donor-acceptor excited complex can be formed between the hole transport compound and the 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 of delayed fluorescence emission from T1 to S1 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.

[0429] In some embodiments, the OLED may include additional compounds selected from the group consisting of: non-delayed fluorescent materials, delayed fluorescent materials, phosphorescent materials, and combinations thereof.

[0430] In some embodiments, the compounds of the invention described herein are phosphorescent materials.

[0431] In some embodiments, the phosphorescent material is an emitter that emits light within the OLED. In some embodiments, the phosphorescent material does not emit light within the OLED. In some embodiments, the phosphorescent material energy transfers its excited state to another material within the OLED. In some embodiments, the phosphorescent material participates in charge transport within the OLED. In some embodiments, the phosphorescent material is a sensitizer or a component of a sensitizer, and the OLED further comprises an acceptor. In some embodiments, the phosphorescent material forms an exciplex with another material (e.g., a host material, an emitter material) within the OLED.

[0432] In some embodiments, the non-delayed fluorescent material or delayed fluorescent material is an emitter that emits light in the OLED. In some embodiments, the non-delayed fluorescent material or delayed fluorescent material does not emit light in the OLED. In some embodiments, the non-delayed fluorescent material or delayed fluorescent material energy transfers its excited state to another material in the OLED. In some embodiments, the non-delayed fluorescent material or delayed fluorescent material participates in charge transport in the OLED. In some embodiments, the non-delayed fluorescent material or delayed fluorescent material is an acceptor, and the OLED further comprises a sensitizer.

[0433] 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 called metal-assisted (MA) TADF). In some embodiments, the metal-assisted delayed fluorescent material comprises a metal-carbenium 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, indolecarbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, 5λ 2 -Benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, 5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene, 5λ 2 ,9λ 2 -diaza-13b-borazinnaphtho[2,3,4-de]anthracene, 5-oxa-9λ 2-aza-13b-borazinnaphtho[3,2,1-de]anthracene, azacyclohexaborane, oxaborin, dihydroacridine, xanthene, dihydrobenzazasilane, dibenzooxasilane, phenoxazine, phenoxathiol, phenothiazine, dihydrophenazine, fluorene, naphthalene, anthracene, phenanthrol, phenanthroline, benzoquinoline, quinoline, isoquinoline, quinazoline, pyrimidine, pyrazine, pyridine, triazine, boryl, amino, silyl, aza variants thereof, and combinations thereof. In some embodiments, the non-delayed fluorescent material or 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.

[0434] In yet another aspect, the OLED of the present disclosure may further comprise an emission region comprising a compound or formulation of compounds disclosed in the above compound section of the present disclosure. In some embodiments, the emission region may comprise a first ligand L comprising formula I A In some embodiments, the emissive region is composed of one or more organic layers, wherein at least one of the one or more organic layers has a minimum thickness selected from the group consisting of: 350, 400, 450, 500, 550, 600, 650, and In some embodiments, at least one of the one or more organic layers is formed of an emissive system having a figure of merit (FOM) equal to or greater than a value selected from the group consisting of: 2.50, 2.55, 2.60, 2.65, 2.70, 2.75, 2.80, 2.85, 2.90, 2.95, 3.00, 5.00, 10.0, 15.0, and 20.0. The definition of FOM can be found in U.S. Patent Application Publication No. 2023 / 0292605, and the entire contents are incorporated herein by reference. In some embodiments, at least one of the one or more organic layers comprises a compound or formulation of a compound disclosed in Sections A and D of the present disclosure.

[0435] In some embodiments, the OLED or emission region 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 includes at least one pixel, wherein the at least one pixel includes a first sub-pixel and a second sub-pixel. The first sub-pixel includes a first OLED including a first emission region. The second sub-pixel includes a second OLED, which includes a second emission region. In some embodiments, the first and / or second OLED, the first and / or second emission region may be the same or different and each may independently have various device features disclosed herein 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.

[0436] 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 With 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 are as described above. In some embodiments, the first emission region is configured to emit a peak wavelength λ max1 Light in one region of the visible spectrum of 400-500nm, 500-600nm, 600-700nm; and the second emission region is configured to emit a peak wavelength λ max2 Light in one of the remaining regions of the visible spectrum of 400-500nm, 500-600nm, 600-700nm. In some embodiments, the first emission region comprises a first number of emission layers, and if there are more than one emission layer, one layer is deposited on another layer; and the second emission region comprises a second number of emission layers, and if there are more than one emission layer, one layer is deposited on another layer; and the first number is different from the second number. In some embodiments, the first emission region and the second emission region both 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, the first emission region and the second emission region both comprise fluorescent materials, which may be the same or different.

[0437] In some embodiments, at least one pixel in an OLED or an emission 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 emission region; wherein the total number of emission regions within at least one pixel is equal to or less than N-1. In some embodiments, the second emission region is identical to the first emission region; and each subpixel of at least one pixel includes an emission region that is identical to the first emission region. In some embodiments, a full-color pixel arrangement may have a plurality of pixels including a first pixel region and a second pixel region; wherein at least one display feature in the first pixel region is different from a corresponding display feature in the second pixel region, and wherein at least one display feature is selected from the group consisting of: resolution, cavity mode, color, outcoupling, and color filter.

[0438] 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 described above for the pixelated device. In some embodiments, the stacked OLED is configured to emit white. In some embodiments, one or more emission regions in the pixelated OLED or stacked OLED include a sensitizer and an acceptor, which have 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.

[0439] In some embodiments, the OLED may emit at least 1%, 5%, 10%, 30%, 50%, 70%, 80%, 90%, 95%, 99%, or 100% of the light having a plasmon mode. In some embodiments, at least one of the anode, cathode, or a new layer disposed above the organic emission layer acts as an enhancement layer. The enhancement layer includes a plasmon material that exhibits a 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 a surface plasmon polariton. In some embodiments, the enhancement layer is disposed at a distance from the organic emission 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 distance at which the total non-radiative decay rate constant is equal to the total radiative decay rate constant. Another threshold distance is the distance at which the total radiative decay rate constant divided by the sum of the total non-radiative decay rate constant and the total radiative decay rate constant is equal to the photoluminescence yield of the emitting material in the absence of the enhancement layer.

[0440] In some embodiments, the OLED further includes an outcoupling layer. In some embodiments, the outcoupling layer is disposed on a side of the enhancement layer opposite to the organic emission layer. The outcoupling layer scatters energy from surface plasmon polaritons. In some embodiments, this energy is dispersed into free space in the form of 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 materials, inorganic materials, perovskites, oxides, and may include stacks and / or mixtures of these materials.

[0441] 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, modification of the emission line shape, changes in emission intensity versus angle, changes in the stability of the emitter material, changes in the efficiency of the OLED, and reduced efficiency decay 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 above effects. In addition to the specific functional layers described in the various OLED examples mentioned herein and shown in the figures, the OLED according to the present disclosure may also include any of the other functional layers typically found in OLEDs.

[0442] 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, Ca alloys, or mixtures of these materials, and stacks of these materials. In some embodiments, the enhancement layer is provided as a flat layer. In other embodiments, the enhancement layer has periodic, quasi-periodic, or randomly arranged wavelength-sized features, or periodic, quasi-periodic, or randomly arranged sub-wavelength-sized features.

[0443] In some embodiments, the outcoupling layer has wavelength-sized features or sub-wavelength-sized features that are arranged periodically, quasi-periodically, or randomly. 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 adjusted by at least one of the following: changing the size of the plurality of nanoparticles, changing the shape of the plurality of nanoparticles, changing the material of the plurality of nanoparticles, adjusting the thickness of the material, changing the refractive index of the material, adding an additional layer disposed on the plurality of nanoparticles, changing the thickness of the enhancement layer, or changing the material of the enhancement layer. The plurality of nanoparticles of the device can be formed by at least one of the following: a metal, a dielectric material, a semiconductor material, a metal alloy, a mixture of dielectric materials, a stack or layering of one or more materials, and / or a core of one type of material, and the core is coated with a shell of a different 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.

[0444] 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.

[0445] In yet another aspect, the present disclosure also provides a consumer product comprising an organic light-emitting device (OLED), the organic light-emitting device 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 compound formulation as disclosed in the above-mentioned compound section of the present disclosure.

[0446] In some embodiments, the consumer product comprises an OLED having an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer may comprise a first ligand L comprising Formula I A of compounds.

[0447] In general, an OLED comprises at least one organic layer disposed between an anode and a cathode and electrically connected to the anode and the cathode. When an electric current is applied, the anode injects holes and the cathode injects electrons into one or more organic layers. The injected holes and electrons each migrate toward the oppositely charged electrode. When electrons and holes are localized on the same molecule, an "exciton" is formed, which is a localized electron-hole pair with an excited energy state. When the exciton relaxes via a photoemission mechanism, light is emitted. In some cases, the exciton can be localized on a quasi-molecule or an excited complex. Non-radiative mechanisms (such as thermal relaxation) may also occur, but are generally considered undesirable.

[0448] Figure 1 An organic light-emitting device 100 is shown. The figures are not necessarily drawn to scale. The 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 emission layer (EML) 135, a hole blocking layer (HBL) 140, an electron transport layer (ETL) 145, an electron injection layer (EIL) 150, a protective layer 155, a cathode 160, and a blocking layer 170. The cathode 160 is a composite cathode having a first conductive layer 162 and a second conductive layer 164. The device 100 can be made by depositing the layers in sequence. The properties and functions of these different layers and example materials are described in more detail in US 7,279,704, columns 6-10, which are incorporated by reference.

[0449] There are more examples of each of these layers. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. Patent No. 5,844,363, which is incorporated by reference in its entirety. An example of a p-doped hole transport layer is m-MTDATA doped with F4-TCNQ at a 50:1 molar ratio, as disclosed in U.S. Patent Application Publication No. 2003 / 0230980, which is incorporated by reference in its entirety. Examples of emissive materials and host materials are disclosed in U.S. Patent No. 6,303,238 to Thompson et al., which is incorporated herein by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li at a 1:1 molar ratio, as disclosed in U.S. Patent Application Publication No. 2003 / 0230980, which is incorporated by reference in its entirety. Examples of cathodes include composite cathodes having a thin layer of metal (e.g., Mg:Ag) overlying a sputter-deposited transparent conductive ITO layer, disclosed in U.S. Pat. Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entirety. The theory and use of barrier layers are described in more detail in U.S. Pat. No. 6,097,147 and U.S. Patent Application Publication No. 2003 / 0230980, which are incorporated by reference in their entirety. 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.

[0450] 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 made by depositing the layers in order. Because the most common OLED configuration has a cathode disposed on the anode, and device 200 has cathode 215 disposed under anode 230, device 200 can be referred to as an "inverted" OLED. Materials similar to those described with respect to device 100 can be used in the corresponding layers of device 200. Figure 2 An example is provided of how some layers may be omitted from the structure of device 100.

[0451] Figure 1 and 2The simple layered structure illustrated in is provided as a non-limiting example, and it should be understood that embodiments of the present disclosure may be used in conjunction with a variety of other structures. The specific materials and structures described are exemplary in nature, and other materials and structures may be used. Functional OLEDs may be achieved by combining the various layers described in different ways, or several 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 various layers as comprising a single material, it should be understood that combinations of materials (e.g., mixtures of a host and a dopant) or, more generally, mixtures may be used. In addition, a layer may have various sublayers. The names given to the various layers herein are not intended to be strictly limiting. For example, in device 200, hole transport layer 225 transports holes and injects holes into emissive layer 220, and may be described as a hole transport layer or a hole injection layer. In one embodiment, the OLED may be described as having an "organic layer" disposed between a cathode and an anode. This organic layer may include a single layer, or may further include, for example, Figure 1 and 2 Multiple layers of said different organic materials.

[0452] Structures and materials not specifically described may also be used, such as OLEDs containing 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 be combined with Figure 1 and 2 For example, the substrate may include angled reflective surfaces to improve out-coupling, such as mesa structures as described in U.S. Pat. No. 6,091,195 to Forrest et al., and / or crater structures as described in U.S. Pat. No. 5,834,893 to Bulovic et al., which are incorporated herein by reference in their entirety.

[0453] 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 (e.g., described in U.S. Pat. Nos. 6,013,982 and 6,087,196, which are incorporated by reference in their entirety), organic vapor phase deposition (OVPD) (e.g., described in U.S. Pat. No. 6,337,102 to Forrest et al., which is incorporated by reference in its entirety), and deposition by organic vapor jet printing (OVJP, also known as organic vapor jet deposition (OVJD)) (e.g., described in U.S. Pat. No. 7,431,968, which is incorporated by reference in its entirety). Other suitable deposition methods include spin coating and other solution-based processes. Solution-based processes are preferably carried out in nitrogen or an inert atmosphere. For other layers, preferred methods include thermal evaporation, sputtering, chemical vapor deposition, atomic layer deposition, and electron beam deposition. Preferred patterning methods include deposition through a mask, photolithography, and cold welding (e.g., as described in U.S. Pat. Nos. 6,294,398 and 6,468,819, which are incorporated by reference in their entirety), as well as patterning associated with some deposition methods such as inkjet and organic vapor jet printing (OVJP). Other methods may also be used. The material to be deposited may be modified to make it compatible with a particular deposition method. For example, substituents such as alkyl and aryl groups, which may be branched or unbranched and preferably contain at least 3 carbons, may be used in small molecules to enhance their ability to withstand solution processing. Substituents having 20 carbons or more may be used, with 3 to 20 carbons being a preferred range. The solution processability of materials having an asymmetric structure may be better than that of materials having a symmetric structure, because asymmetric materials may have a lower tendency to recrystallize. Dendritic polymer substituents may be used to enhance the ability of small molecules to withstand solution processing.

[0454] Devices manufactured according to 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 exposure to harmful substances in an environment including moisture, vapor and / or gas, etc. The barrier layer may be deposited on a substrate, above an electrode, under a substrate, or next to a substrate, an electrode, or on any other part of the device (including an edge). The barrier layer may include a single layer or multiple layers. The barrier layer may be formed by various known chemical vapor deposition techniques and may include compositions having a single phase and compositions having multiple phases. Any suitable material or combination of materials may be used for the barrier layer. The barrier layer may be combined with an inorganic compound or an organic compound or both. Preferred barrier layers include multiple alternate layers of the following materials: polymeric materials and non-polymeric materials; organic materials and inorganic materials; or a mixture of polymeric materials and non-polymeric materials, an example of which is described in U.S. Patent No. 7,968,146, PCT Patent Application Nos. PCT / US2007 / 023098 and PCT / US2009 / 042829, which are incorporated herein by reference in their entirety.

[0455] The devices manufactured according to the embodiments of the present disclosure can be incorporated into a variety of electronic component modules (or units), which can be incorporated into a variety of electronic products or intermediate components. Examples of such electronic products or intermediate components include display screens, lighting devices (such as discrete light source devices or lighting panels), etc. that can be utilized by end-user product manufacturers. The electronic component module may optionally include driving electronics and / or a power supply. The devices made according to the embodiments of the present disclosure can be incorporated into a variety of consumer products, and one or more electronic component modules (or units) are included in the consumer products. A consumer product comprising an OLED is disclosed, and the organic layer of the OLED includes a compound of the present disclosure. Such consumer products should include any kind of product containing one or more light sources and / or a certain 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, mobile 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 matrices and active matrices. Many devices are intended to be used within 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).

[0456] More details regarding OLEDs and the above definitions can be found in US Pat. No. 7,279,704, which is incorporated herein by reference in its entirety.

[0457] The materials and structures described herein can be applied to devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors can use the materials and structures. More generally, organic devices such as organic transistors can employ the materials and structures.

[0458] In some embodiments, the OLED has one or more features selected from the group consisting of: flexible, rollable, foldable, stretchable, and bendable. In some embodiments, the OLED is transparent or 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. The quantum dots may be in the emission layer, or in other functional layers, such as downconversion layers.

[0459] 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.

[0460] D. Other materials used in OLED

[0461] As various examples, the materials described herein are suitable for use in specific layers in an OLED. They may also be used in combination with a variety of other materials present in the device. For example, the emissive dopants disclosed herein may 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 may be used in combination with the compounds and devices disclosed herein, and those skilled in the art may readily consult the literature to identify other materials that may be used in combination.

[0462] a) Conductive dopants:

[0463] 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.

[0464] b)HIL / HTL:

[0465] 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; indolecarbazole derivatives; polymers containing fluorocarbons; polymers having a conductive dopant; conductive polymers such as PEDOT / PSS; self-assembling monomers derived from compounds such as phosphonic acid and silane derivatives; metal oxide derivatives such as MoO x ; p-type semiconductive organic compounds, such as 1,4,5,8,9,12-hexaazatriphenylenehexacarbonitrile; metal complexes; and crosslinkable compounds.

[0466] Examples of aromatic amine derivatives used in HIL or HTL include, but are not limited to, the following general structure:

[0467]

[0468] Ar 1 To Ar 9 Each of the compounds is selected from the group consisting of aromatic hydrocarbon ring compounds, such as benzene, biphenyl, terphenyl, triphenylene, naphthalene, anthracene, phenanthrene, fluorene, pyrene, Perylene and azulene; the group consisting of aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridyl indole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indolizine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxoline , naphthyridine, phthalazine, pteridine, dibenzopyran, acridine, phenazine, phenothiazine, phenoxazine, benzofuranopyridine, furanodipyridine, 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 directly bonded to each other or bonded via at least one of oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms, phosphorus atoms, boron atoms, chain structural units and aliphatic ring groups. Ar 1 To Ar 9 Each of may be unsubstituted or may be substituted with the general substituents described above, and any two substituents may be joined or fused to form a ring.

[0469] In some embodiments, each Ar 1 To Ar 9 independently comprising a portion selected from the group consisting of:

[0470]

[0471] Wherein k is an integer from 1 to 20; X 101 To X 108 is C or N; Z 101 is C, N, O or S.

[0472] Examples of metal complexes used in HIL or HTL include, but are not limited to, the following general formula:

[0473]

[0474] Where 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.

[0475] In some embodiments, (Y 101 -Y 102 ) is a 2-phenylpyridine or 2-phenylimidazole derivative. In some embodiments, (Y 101 -Y 102 ) is a carbene ligand. In some embodiments, Met is selected from Ir, Pt, Pd, Os, Cu and Zn. In some embodiments, the metal complex is in solution relative to Fc + The / Fc pair has a minimum oxidation potential of less than about 0.6V.

[0476] In some embodiments, the HIL / HTL material is selected from the group consisting of phthalocyanine and porphyrin compounds, starburst triarylamines, CF x Fluorocarbon polymers, conductive polymers (e.g., PEDOT:PSS, polyaniline, polythiophene), phosphonic acid and silane SAMs, triarylamine or polythiophene polymers containing conductive dopants, organic compounds containing conductive inorganic compounds (e.g., molybdenum oxide and tungsten oxide), n-type semiconductive organic complexes, metal organic metal complexes, crosslinkable compounds, polymers and copolymers based on polythiophene, triarylamines, triarylamines containing spirofluorene cores, arylamine carbazole compounds, triarylamines containing (di)benzothiophene / (di)benzofuran, indolecarbazoles, isoindole compounds, and metal carbene complexes.

[0477] c) EBL:

[0478] An electron blocking layer (EBL) can be used to reduce the number of electrons and / or excitons leaving the emissive layer. The presence of such a blocking layer in the device can result in significantly improved efficiency and / or longer lifetime compared to similar devices lacking a blocking layer. In addition, a blocking layer can be used to confine emission to a desired area of ​​the OLED. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and / or a higher triplet energy than one or more 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 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.

[0479] d) Subject:

[0480] 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.

[0481] Examples of metal complexes used as hosts preferably have the following general formula:

[0482]

[0483] Where 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.

[0484] In some embodiments, the metal complex is:

[0485]

[0486] where (ON) is a bidentate ligand with a metal coordinated to O and N atoms.

[0487] In some embodiments, Met is selected from Ir and Pt. In another embodiment, (Y 103 -Y 104 ) is a carbene ligand.

[0488] In some embodiments, the host compound contains at least one group selected from the group consisting of aromatic hydrocarbon cyclic compounds, such as benzene, biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenanthrene, fluorene, pyrene, Perylene and azulene; the group consisting of aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridyl indole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine , indole, benzimidazole, indazole, indoloxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, dibenzopyran, acridine, phenazine, phenothiazine, phenoxazine, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, aza-carbazole, aza-indolocarbazole, aza-triphenylene, aza-tetraphenylene, 5λ 2 -benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, 5,9-dioxa-13b-borazinnaphtho[3,2,1-de]anthracene; and a group consisting of 2 to 10 cyclic structural units, the cyclic structural units are groups of the same type or different types, which are selected from aromatic hydrocarbon ring groups and aromatic heterocyclic groups and are directly bonded to each other or bonded via at least one of oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms, phosphorus atoms, boron atoms, chain structural units and aliphatic ring groups. Each option within each group may be unsubstituted or may be substituted by the general substituents described herein or may be further condensed.

[0489] In some embodiments, the host compound comprises at least one chemical moiety selected from the group consisting of:

[0490]

[0491]

[0492] wherein k is an integer from 0 to 20 or from 1 to 20. 101 To X 108 Z is independently selected from C or N. 101 and Z 102 are independently selected from C, N, O or S.

[0493] In some embodiments, the host material is selected from the group consisting of: aryl carbazoles, metal 8-hydroxyquinolinates (e.g., alq3, balq), metal phenoxybenzothiazole compounds, conjugated oligomers and polymers (e.g., polyfluorene), aromatic fused rings, zinc complexes, Compounds, aryltriphenylene compounds, poly-condensed 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 with N^N ligands), dibenzothiophene / dibenzofuran-carbazole compounds, silicon / germanium aryl compounds, arylbenzoyl esters, carbazoles connected by non-conjugated groups, aza-carbazole / dibenzofuran / dibenzothiophene compounds, and high triplet metal organic metal complexes (e.g., metal-carbene complexes).

[0494] e) Emitter materials in EML:

[0495] One or more emitter materials can be used in combination with the compounds or devices disclosed herein. The emitter material can be an emitting or non-emitting material in the current device described herein. The examples of emitter materials are not particularly limited, and any compound can be used as long as the compound can produce emission in a conventional OLED device. Examples of suitable emitter materials include, but are not limited to, compounds that can produce 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 processes.

[0496] In some embodiments, the emitter material has the formula M(L 1 ) x (L 2 ) y (L 3 ) z ;

[0497] Where L 1 , L 2 and L 3 Can be the same or different;

[0498] where x is 1, 2, or 3;

[0499] Where y is 0, 1 or 2;

[0500] where z is 0, 1 or 2;

[0501] Wherein x+y+z is the oxidation state of the metal M;

[0502] Where L 1 Selected from the group consisting of structures in the following ligand list:

[0503]

[0504]

[0505]

[0506] Among them, each L 2 and L 3 Independently selected from the group consisting of: and a structure from the ligand list; where:

[0507] M is selected from the group consisting of Ir, Rh, Re, Ru, Os, Pt, Pd, Zn, Au, Ag and Cu;

[0508] T is selected from the group consisting of B, Al, Ga and In;

[0509] K 1' Is a direct key or selected from NR e , PR e , O, S and Se;

[0510] Each Y 1 To Y 15 independently selected from the group consisting of carbon and nitrogen;

[0511] Y' is selected from the group consisting of: BR e NR e , PR e ,O,S,Se,C=O,S=O,SO2,CR e R f 、SiR e R f and GeR e R f ;

[0512] Each R a , R b , R c and R d can independently represent a single substitution to the maximum possible number of substitutions, or no substitution;

[0513] 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

[0514] Any two of the substituents may be fused or joined to form a ring or to form a polydentate ligand.

[0515] In some embodiments, the emitter material is selected from the group consisting of the following dopant group 1:

[0516]

[0517]

[0518]

[0519]

[0520]

[0521] in

[0522] X 96 To X 99 Each of is independently C or N;

[0523] Each Y 100 Independently selected from the group consisting of NR", O, S and Se;

[0524] R 10a , R 20a , R 30a , R 40a and R 50a Each of the above independently represents a single substitution up to a maximum number of substitutions, or no substitution;

[0525] R, R', R", R 10a , R 11a , R 12a , R 13a , R 20a , R 30a , R 40a , R 50a , R 60 , R 70 , R 97 , R 98 and R 99 Each of is independently hydrogen or a substituent selected from the group consisting of general substituents defined herein; any two substituents may be joined or fused to form a ring.

[0526] In some embodiments, the emitter material is selected from the group consisting of the following dopant group 2:

[0527]

[0528]

[0529]

[0530]

[0531]

[0532]

[0533]

[0534]

[0535] in:

[0536] Each Y 100 Independently selected from the group consisting of NR", O, S and Se;

[0537] 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;

[0538] X 100 and X 200 At each occurrence, selected from the group consisting of O, S, Se, NR", and CR"R'";

[0539] Each R A" , R B" , R C" , R D" , R E" and R F" independently represents a single substitution up to the maximum number of substitutions, or no substitution;

[0540] 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 defined herein; any two substituents may be joined or fused to form a ring.

[0541] In some embodiments of the above dopant groups 1 and 2, each unsubstituted aromatic carbon atom may be replaced by N to form a nitrogen heterocycle. In some embodiments, the maximum number of N atoms in one ring is 1 or 2. In some embodiments of the above dopant group 2, the Pt atoms in each formula may be replaced by Pd atoms.

[0542] In some embodiments of 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 Zn, Cu, Ag or Au complex.

[0543] In some embodiments of OLEDs, the delayed fluorescent material has the formula M(L 5 )(L 6 ), where 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:

[0544]

[0545]

[0546]

[0547] Among them A 1 To A 9 are each independently selected from C or N;

[0548] Each R P , R Q and R U independently represents a single substitution up to the maximum number of substitutions, or no substitution;

[0549] Among them, each R P , R P , R U , R SA , R SB , R RA , R RB , R RC , R RD , R RE and R RF is independently hydrogen or a substituent selected from the group consisting of general substituents defined herein; any two substituents may be joined or fused to form a ring.

[0550] In some embodiments of the OLED, the delayed fluorescent material comprises at least one donor moiety selected from the group consisting of:

[0551]

[0552]

[0553] 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.

[0554] In some of the above embodiments, any carbon ring atom, up to a total of three carbon ring atoms together with their substituents, in each benzene ring of any of the above structures can be replaced by N.

[0555] 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 (such as sp 3 carbon or silicon atoms).

[0556] In some embodiments, the fluorescent material comprises at least one chemical moiety selected from the group consisting of:

[0557]

[0558]

[0559]

[0560] 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;

[0561] Where X F and X G are each independently selected from the group consisting of C and N.

[0562] In some of the above embodiments, any carbon ring atom, up to a total of three carbon ring atoms together with their substituents, in each benzene ring of any of the above structures can be replaced by N.

[0563] f)HBL:

[0564] A hole blocking layer (HBL) can be used to reduce the number of holes and / or excitons that leave the emissive layer. The presence of the blocking layer in the device can result in substantially higher efficiency and / or longer lifetime than a similar device lacking the blocking layer. In addition, the blocking layer can be used to confine emission to a desired area 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 emitters closest to the HBL interface.

[0565] In some embodiments, the compound used in HBL contains the same molecule or the same functional group as used in the above-mentioned subject.

[0566] In some embodiments, the compound used in HBL comprises at least one chemical moiety selected from the group consisting of:

[0567]

[0568] wherein k is an integer from 1 to 20; L 101 is another ligand, and k' is an integer from 1 to 3.

[0569] g)ETL:

[0570] 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 composite or organic compound may be used as long as it is typically used to transport electrons.

[0571] In some embodiments, the compounds used in the ETL contain at least one of the following moieties in the molecule:

[0572]

[0573] 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.

[0574] In some embodiments, the metal complex used in the ETL contains but is not limited to the following general formula:

[0575]

[0576] 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.

[0577] 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), thiole compounds, arylborane compounds, fluorinated aromatic compounds, fullerenes (e.g., C60), triazine complexes, and Zn(N^N) complexes.

[0578] h) Charge Generation Layer (CGL)

[0579] In a tandem or stacked OLED, the CGL plays an important role in performance and is composed 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. The electrons and holes consumed in the CGL are refilled by electrons and holes injected from the cathode and anode, respectively; then, the bipolar current gradually reaches a steady state. Typical CGL materials include n and p conductivity dopants used in the transport layer.

[0580] In any compound disclosed herein, hydrogen atoms 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, the deuteration percentage has its common 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.

[0581] It should be understood that the various embodiments described herein are only for example, and are not intended to limit the scope of the present invention. For example, many of the materials and structures described herein can be replaced with other materials and structures without departing from the spirit of the present invention. The present invention as required can therefore 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.

[0582] E. Experimental Data

[0583]

[0584] Synthesis of N-(2-bromo-6-nitrophenyl)-[1,1':3',1"-terphenyl]-2,2",3,3",4,4",5,5",6,6"-d 10 -2'-Amine

[0585] A solution of [1,1':3',1"-terphenyl]-2,2",3,3",4,4",5,5",6,6"-d10-2'-amine (6.5 g, 25.5 mmol, 1.0 equiv) in THF (50 mL) was cooled to -78 °C in a 250 mL round bottom flask in a dry ice bath and bubbled with nitrogen for 10 min. A 1 M solution of lithium bis(trimethylsilyl)amide in THF (50.9 mL, 50.9 mmol, 2.0 equiv) was added via syringe over 30 min, resulting in a yellow solution which formed a precipitate shortly thereafter. The resulting suspension was removed from the cooling bath and stirred at room temperature for 30 min. The suspension was cooled to -78 °C in a dry ice bath, and a solution of 1-bromo-2-fluoro-3-nitrobenzene (6.2 g, 28.0 mmol, 1.1 equiv) in anhydrous THF (25 mL) was added via a syringe over 10 minutes. The reaction mixture was warmed to room temperature and stirred for 16 hours. The reaction mixture was cooled in an ice bath and quenched with methanol (15 mL). The resulting solution was evaporated and triturated with hexane to give N-(2-bromo-6-nitrophenyl)-[1,1':3',1"-terphenyl]-2,2",3,3",4,4",5,5",6,6"-d as an orange solid. 10 -2'-amine (8.8 g, 76% yield).

[0586] Synthesis of N1-([1,1':3',1"-terphenyl]-2'-yl-2,2",3,3",4,4",5,5",6,6"-d 10 )-6-Bromobenzene-1,2-diamine

[0587] N-(2-bromo-6-nitrophenyl)-[1,1':3',1"-terphenyl]-2,2",3,3",4,4",5,5",6,6"-d 10-2'-amine (10.0g, 22.0mmol, 1.0 equivalent) and zinc powder (7.2g, 109.8mmol, 6.0 equivalent) in a mixture of THF (100mL) and glacial acetic acid (50mL) were stirred at room temperature for 16 hours. The reaction mixture was filtered through a Celite plug and washed with dichloromethane. The filtrate was concentrated and extracted with ethyl acetate and brine. The organic layer was dehydrated with sodium sulfate and evaporated to dryness to obtain N1-([1,1':3',1"-terphenyl]-2'-base-2,2",3,3",4,4",5,5",6,6"-d in an off-white solid state. 10 )-6-bromobenzene-1,2-diamine (7.2 g, 77% yield).

[0588] Synthesis of N2-([1,1':3',1"-terphenyl]-2'-yl-2,2",3,3",4,4",5,5",6,6"-d 10 )-3-bromo-N1-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)benzene-1,2-diamine

[0589] N1-([1,1':3',1"-terphenyl]-2'-yl-2,2",3,3",4,4",5,5",6,6"-d 10 A solution of )-6-bromobenzene-1,2-diamine (8.7 g, 40.7 mmol, 1.0 equiv), 2-(3-bromophenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazole (10.6 g, 22.5 mmol, 1.1 equiv) and BINAP Pd Gen3 (3.0 g, 3.1 mmol, 0.15 equiv) in anhydrous toluene (100 mL) was bubbled with nitrogen for 15 minutes. Sodium tert-butoxide (5.9 g, 61.3 mmol, 3.0 equiv) was added in one portion and the reaction mixture was heated at 100 °C for 16 hours. The reaction mixture was cooled to room temperature and filtered through a plug of celite and extracted with ethyl acetate and brine. The crude material was chromatographed on silica eluting with 50% dichloromethane / hexanes to afford N2-([1,1':3',1"-terphenyl]-2'-yl-2,2",3,3",4,4",5,5",6,6"-d as a yellow foam. 10 )-3-bromo-N1-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)benzene-1,2-diamine (10.9 g, 65% yield).

[0590] Synthesis of 3-([1,1':3',1"-terphenyl]-2'-yl-2,2",3,3",4,4",5,5",6,6"-d 10)-4-bromo-1-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-2,3-dihydro-1H-benzo[d]imidazolium chloride

[0591] N2-([1,1':3',1"-terphenyl]-2'-yl-2,2",3,3",4,4",5,5",6,6"-d 10 A mixture of )-3-bromo-N1-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)benzene-1,2-diamine (10.8 g, 13.2 mmol, 1.0 equiv), triethyl orthoformate (66 mL, 397.0 mmol, 30 equiv) and concentrated HCl (3.4 mL, 39.7 mmol, 3.0 equiv) was heated at 80 °C for 16 hours. The reaction mixture was cooled to room temperature and concentrated under reduced pressure. The crude product was dissolved in dichloromethane (10 mL) and diluted with diethyl ether (300 mL). The resulting solid was filtered to give 3-([1,1':3',1"-terphenyl]-2'-yl-2,2",3,3",4,4",5,5",6,6"-d as a white solid. 10 )-4-bromo-1-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-2,3-dihydro-1H-benzo[d]imidazolium chloride (10.4 g, 91% yield).

[0592] Synthesis of Br-Pt precursor

[0593] 3-([1,1':3',1"-terphenyl]-2'-yl-2,2",3,3",4,4",5,5",6,6"-d 10 A solution of 4-bromo-1-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-2,3-dihydro-1H-benzo[d]imidazolium chloride (9.4 g, 10.9 mmol, 1.0 equiv), Pt precursor (1.0 equiv) and base (3.0 equiv) in an organic solvent (50 mL) was heated at 110 °C for 72 h. The reaction mixture was cooled to room temperature and diluted with methanol (100 mL). The solid was triturated in a 2:1 mixture of methanol and dichloromethane (20 mL), filtered and dried under vacuum to give the Br-Pt precursor (9.5 g, 85% yield) as a yellow solid.

[0594] Synthesis of Emitter-1

[0595] A solution of phenyl-d5-bromide (540 mg, 3.3 mmol, 2.0 equiv) in anhydrous THF (4 mL) was cooled in a dry ice bath and bubbled with nitrogen for 2 minutes. 1.6 M n-butyl lithium in THF (2.1 mL, 3.3 mmol, 2.0 equiv) was added dropwise via a syringe and stirred for 2 hours, at which time a white precipitate was formed. 1.9 M zinc chloride in dioxane (1.8 mL, 3.3 mmol, 2.0 equiv) was added in one go. The reaction mixture was allowed to warm to room temperature and stirred for 10 minutes to form a clear solution of phenyl-d5-zinc chloride. A solution of Br-Pt precursor (1.7 g, 1.7 mmol, 1.0 equiv) and SPhos PdGen2 (120 mg, 0.17 mmol, 0.1 equiv) in anhydrous dioxane (5 mL) was bubbled with nitrogen for 3 minutes. Phenyl-d5-zinc chloride solution was added via a syringe and the reaction mixture was heated to 80 ° C for 16 hours. The reaction mixture was cooled to room temperature, quenched with methanol (0.5 mL) and evaporated to dryness under reduced pressure. The crude material was chromatographed on silica, eluted with 50% dichloromethane / hexane. The product was wet-triturated to give emitter-1 (1.2 g, 70% yield) as a yellow solid.

[0596] Synthesis of Emitter-2

[0597] A solution of 6-bromo-1,1,4,4-tetrakis(methyl-d3)-1,2,3,4-tetrahydronaphthalene-2,2,3,3,5,7,8-d7 (1.2 g, 4.1 mmol, 4.0 equiv) in anhydrous THF (5 mL) was cooled in a dry ice bath and bubbled with nitrogen for 5 minutes. 1.6 M n-butyllithium in THF (2.6 mL, 4.1 mmol, 4.0 equiv) was added dropwise via a syringe over 10 minutes. After stirring for 2 hours, a white precipitate was formed. 1.9 M zinc chloride in dioxane (2.2 mL, 4.1 mmol, 4.0 equiv) was added in one portion. The reaction mixture was allowed to warm to room temperature and stirred for 10 minutes to form a clear solution of the corresponding arylzinc chloride. A solution of Br-Pt precursor (1.0 g, 1.0 mmol, 1.0 equiv) and P(tBu)3PdGen3 (118 mg, 0.2 mmol, 0.2 equiv) in anhydrous dioxane (5 mL) was bubbled with nitrogen for 5 minutes. Aryl zinc chloride solution was added via a syringe and the reaction mixture was heated to 80 ° C for 16 hours to form a dark solution. The reaction mixture was cooled to room temperature, quenched with methanol (0.5 mL) and evaporated to dryness under reduced pressure. The crude material was chromatographed on silica gel, eluted with 50% dichloromethane / hexane. The product was wet-triturated with methanol to give emitter-2 (750 mg, 64% yield) as a yellow solid.

[0598] Synthesis of Emitter-3

[0599] A solution of Br-Pt precursor (1.1 g, 1.1 mmol, 1.0 equiv) and P(tBu)3PdGen3 (61 mg, 0.1 mmol, 0.1 equiv) in anhydrous dioxane (5 mL) was bubbled with nitrogen for 5 minutes. 0.5 M neopentylzinc bromide in THF (4.3 mL, 2.2 mmol, 2.0 equiv) was added via a syringe and the reaction mixture was heated to 80 ° C (external) for 16 hours. The reaction mixture was cooled to room temperature, quenched with methanol (0.5 mL) and evaporated to dryness under reduced pressure. The crude material was chromatographed on silica, eluting with 50% dichloromethane / hexanes. The product was triturated with methanol to give emitter-3 (900 mg, 82% yield) as a yellow solid.

[0600] Table 1. Device performance

[0601] Emitter <![CDATA[At 10 mA / cm 2 under]]> 1. λmax EQE 1. [nm] [Nominal] Emitter-1 463 1.03 Projectile-2 463 1.09 Projectile-3 463 1.01 Comparative Examples 463 1.00

[0602] OLEDs were grown on glass substrates pre-coated with a 15-Ω / sq indium tin oxide (ITO) layer. Prior to any organic layer deposition or coating, the substrates were degreased with solvents and then treated with oxygen plasma at 100 mTorr, 50 W for 1.5 min and UV ozone for 5 min.

[0603] In high vacuum (<10 -6 The devices in Table 1 were fabricated by thermal evaporation in 2000 × ...1000 mm (1200 × 1000 mm) of 1000 mm. The anode electrode was Indium tin oxide (ITO). Starting from the ITO surface, the organic layers of the device example are composed of the following in order: Compound 1 (HIL), Compound 2 (HTL), Compound 3 (EBL), Compound 3 doped with 50% compound 5 and 12% emitter (EML), Compound 4 (BL), Compound 5 doped with 35% of compound 6 (ETL), Compound 5 (EIL), followed by of Al (cathode). All devices were packaged with glass lids and sealed with epoxy resin in a nitrogen glove box (H2O and O2 <1 ppm) immediately after fabrication, with a dehumidifier incorporated inside the package. Doping percentages are volume percentages.

[0604]

[0605]

[0606] The OLED devices detailed in Table 1 provide a 2 Below is an overview of the color and external quantum efficiency (EQE) measured for the compounds of the present invention and the comparative examples. All compounds exhibit very similar EL wavelengths. All compounds of the present invention exhibit higher EQEs compared to the comparative examples. It is believed that this is due to the presence of specific groups of these compounds of the present invention, and the specific groups suppress the molecular electronic vibration modes that cause thermal relaxation and / or reduce the host / dopant interactions caused by additional bulky groups in the device. These improvements exceed any values ​​attributable to experimental errors, and the observed improvements are significant and unexpected. These improved properties are desirable qualities for commercial OLED products.

Claims

1. A compound comprising a first ligand L of formula I A : in: X 1 To X 7 each independently is C or N; K 1 Selected from the group consisting of: direct key, O, S, N(R α )、P(R α )、B(R α )、C(R α )(R β ) and Si(R α )(R β ); R A , R B and R C Each of the above independently represents a single substitution to the maximum number of substitutions allowed, or no substitution; Each R 1 and R 2 are independently substituents selected from the group consisting of halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boryl, aralkyl, alkoxy, aryloxy, amino, silyl, germyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thiol, sulfinyl, sulfonyl, phosphino, selenoalkyl, and combinations thereof; Each R 3 , R 4 , R 5 , R α , R β , R A , R B and R C are independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boryl, aralkyl, alkoxy, aryloxy, amino, silanyl, germanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thiol, sulfinyl, sulfonyl, phosphino, selenanyl, and combinations thereof; L A Coordinate with metal M; M is selected from the group consisting of Ru, Os, Ir, Pd, Pt, Cu, Ag and Au; L A Can be combined with other ligands to form tridentate, tetradentate, pentadentate or hexadentate ligands; Any two substituents may be joined or fused to form a ring; When R1 is substituted or unsubstituted aryl, at least one of the following statements is true: 1.R 1 Contains fused rings, 2.R 2 is a substituted aryl group and contains a fused ring, 3. At least one R A Not hydrogen, 4.R 2 It is Formula II: And (i) R 3 With R 4 Different, (ii) R 5 is not hydrogen, or (iii) both conditions (i) and (ii), and 5.R 2 is Formula II, R 3 is phenyl or d 5 -phenyl, and R 3 With R 4 different; When R 1 is an alkyl group, at least one of the following statements is true: a 2 is Formula II, R 3 is not hydrogen or 3,5-di-tert-butylphenyl, and R 3 With R 4 different, B R 2 is Formula II and R 5 is not hydrogen, and C 1 With R 2 Fused together.

2. The compound according to claim 1, wherein X 1 To X 7 Each of which is C or X 1 To X 7 At least one of is N; and / or Where K 1 is a direct key, O or S; and / or Where R 1 contains an aryl or heteroaryl moiety; and / or wherein R 2 contains an aryl or heteroaryl moiety; and / or wherein R 1 With R 2 the same or different; and / or wherein R 1 and R 2 Fused together to form a ring 12 .

3. The compound according to claim 1, wherein the ligand L A Select from the group consisting of: Where R AA and R D Each of the above independently represents a single substitution to the maximum number of substitutions allowed, or no substitution; Each R AA , R A1 , R A2 , R A3 and R D are independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boryl, aralkyl, alkoxy, aryloxy, amino, silanyl, germanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thiol, sulfinyl, sulfonyl, phosphino, selenanyl, and combinations thereof; The remaining variables are the same as defined previously; and Any two substituents may be optionally fused or joined to form a ring.

4. The compound according to claim 1, wherein the ligand L A Choose from L Ai -(Ri')(Rj')(Rk')(Rl'), wherein i is an integer from 1 to 19, and each of i', j', k' and l' is independently an integer from 1 to 135, except for the following: wherein, When i is 1, 2 or 3, i' and k' are different and / or j' is not 1; wherein, when i is 1, 2 or 3, if i'=27 or 28, then i' and k' are different; wherein, when i is 8, 9 or 10, l' is not 1; wherein, when i is 11, i' is not 1 or 41, and i' and k' are different, or j' is not 1; and L A1 -(R1)(R1)(R1)(R1) to L A19 Each of -(R135)(R135)(R135)(R135) is defined as follows: and Wherein R1 to R135 have the following structure:

5. The compound according to claim 1, wherein the compound has the formula M(L A ) p (L B ) q (L C ) r , where L B and L C Each is a bidentate ligand; and wherein p is 1, 2 or 3; q is 0, 1 or 2; r is 0, 1 or 2; and p+q+r is the oxidation state of the metal M.

6. The compound according to claim 5, wherein the compound has a formula selected from the group consisting of: Ir(L A )3、Ir(L A )(L B )2、Ir(L A )2(L B )、Ir(L A )2(L C ) and Ir(L A )(L B )(L C ); and where L A , L B and L C Different from each other; or formula Pt(L A )(L B ); and where L A and L B Can be the same or different.

7. The compound according to claim 5, wherein L B and L C Each independently selected from the group consisting of: in: T is selected from the group consisting of B, Al, Ga and In; K 1 'Selected from the group consisting of: single bond, O, S, NR e , PR e , BR e , CR e R f and SiR e R f ; Y 1 To Y 13 Each of which is independently selected from the group consisting of C and N; Y'Select from the group consisting of: BR e , BR e R f NR e , PR e 、P(O)R e ,O,S,Se,C=O,C=S,C=Se,C=NR e 、C=CR e R f 、S=O、SO2、CR e R f 、SiR e R f and GeR e R f ; R e With R f may be fused or joined to form a ring; Each R a , R b , R c and R d independently represent mono-substitution to the maximum allowed number of substitutions, or no substitution; R a1 , R b1 , R c1 , R d1 , R a , R b , R c , R d , R e and R f each of which is independently hydrogen or a substituent selected from the group consisting of deuterium, halide, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, germanyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thiol, selenanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and R a1 , R b1 , R c1 , R d1 , R a , R b , R c and R d Any two substituents of may be fused or joined to form a ring or to form a multidentate ligand.

8. The compound according to claim 5, wherein the compound has the formula Ir(L A )3, Formula Ir(L A )(L Bk )2, Formula Ir(L A )2(L Bk ), formula Ir(L A )2(L Cj-I ) or formula Ir(L A )2(L Cj-II ), Where L A It can be L A1 -(R1)(R1)(R1)(R1) to L A19 - one of (R135)(R135)(R135)(R135); Where k is an integer from 1 to 522, and each L Bk The structure is defined as follows: Among them, each L Cj-I Has a structure based on the formula: and Each L Cj-II Has a structure based on the following formula: For L Cj-I and L Cj-II Each L in Cj For example, R 201 and R 202 The definition is as follows: Where R D1 To R D246 Has the following structure:

9. The compound according to claim 5, wherein the compound has formula III: in: M 1 is Pd or Pt; Moieties E and F are each independently a monocyclic or polycyclic ring structure comprising a 5-membered and / or 6-membered carbocyclic or heterocyclic ring; Z 1 and Z 2 each independently is C or N; K 1 ' and K 2 ' are independently selected from the group consisting of direct bonds, O and S, wherein K 1 , K 1 ' and K 2 At least two of ' are direct keys; L 1 and L 2 Each is independently selected from the group consisting of a direct bond, BR, BRR', NR, PR, P(O)R, O, S, Se, C=O, C=S, C=Se, C=NR, C=CRR', S=O, SO2, CR, CRR', SiRR', GeRR', alkylene, cycloalkyl, aryl, cycloalkylene, arylene, heteroarylene, and combinations thereof; R E and R F Each independently represents zero substitution, monosubstitution or up to the maximum allowed number of substitutions on the ring to which it is connected; R, R', R E and R F each of which is independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boryl, aralkyl, alkoxy, aryloxy, amino, silanyl, germanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thiol, sulfinyl, sulfonyl, phosphino, selenanyl, and combinations thereof; and When chemically feasible, two adjacent R A , R B , R C , R E and R F May be joined or fused together to form a ring.

10. The compound according to claim 9, wherein the compound has the formula XA: Or XB: Where X 30 To X 32 each independently is C or N; R E ' indicates single substitution to the maximum number of substitutions allowed, or no substitution; R E '、R EE0 , R EE1 and R EE2 each of which is independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boryl, aralkyl, alkoxy, aryloxy, amino, silanyl, germanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thiol, sulfinyl, sulfonyl, phosphino, selenanyl, and combinations thereof; and Any two substituents may be joined or fused to form a ring.

11. The compound according to claim 9, wherein the compound is selected from the group consisting of A' The group consisting of compounds of )(Ly): Where L A' Select from the group consisting of: Wherein Ly is selected from the group consisting of: Where R AA and R D Each of the above independently represents a single substitution to the maximum number of substitutions allowed, or no substitution; Among them, each R AA , R D , R X and R Y are independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boryl, aralkyl, alkoxy, aryloxy, amino, silanyl, germanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thiol, sulfinyl, sulfonyl, phosphino, selenanyl, and combinations thereof; and Any two substituents therein may be optionally fused or joined to form a ring.

12. The compound according to claim 9, wherein the compound is selected from the group consisting of A' The group consisting of compounds of )(Ly): Where L A' Choose from L A' m-(Rs)(Rt)(Ru)(Rv), wherein m is an integer from 1 to 19, and each of s, t, u and v is independently an integer from 1 to 135, except for the following: wherein, When m is 1, 2 or 3, s and u are different and / or t is not 1; wherein, when m is 1, 2 or 3, if s=27 or 28, then s and u are different; wherein, when m is 8, 9 or 10, v is not 1; Wherein, when m is 11, s is not 1 or 41, and s and u are different, or t is not 1; and L A'1 -(R1)(R1)(R1)(R1) to L A'19 Each of -(R135)(R135)(R135)(R135) is defined as follows: Where L y Choose from L y j-(Rs)(Rt)(Ru)(Rv), wherein j is an integer from 1 to 33, wherein each of s, t and u is independently an integer from 1 to 135, and L y 1-(R1)(R1)(R1) to L y Each of 33-(R135)(R135)(R135) is defined as follows:

13. The compound of claim 9, wherein the compound is selected from the group consisting of: wherein Ph represents phenyl.

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

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

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