Organic electroluminescent materials and devices

Abstract

The invention relates to organic electroluminescent materials and devices. Metal complexes of Formula I and metal complexes of Formula VII are provided. Formulations comprising these metal complexes are also provided. Also provided are OLEDs and related consumer products utilizing these metal complexes. # imgabs0 #

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority under 35 U.S.C. §119(e) to U.S. Provisional Application No. 63 / 514,892, filed on July 21, 2023, the entire contents of which are incorporated herein by reference.

[0003] STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

[0004] This invention was made with government support under Grant No. EE0009688 awarded by the US Department of Energy. The government has certain rights in this invention. Technical Field

[0005] The present disclosure relates generally to organometallic compounds and formulations and various uses thereof, including as emitters in devices such as organic light emitting diodes and related electronic devices. Background Art

[0006] For various reasons, optoelectronic devices utilizing organic materials are becoming increasingly desirable. Many materials used to manufacture such devices are relatively inexpensive, 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, and organic photodetectors. For OLEDs, organic materials can have performance advantages over conventional materials.

[0007] OLEDs utilize organic thin films that emit light when a voltage is applied across the device. OLEDs are becoming an increasingly attractive technology for use in applications such as flat panel displays, lighting, and backlighting.

[0008] One application of phosphorescent emitting 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

[0009] In one aspect, the present disclosure provides a metal complex of Formula I:

[0010]

[0011] in

[0012] Y is N or B;

[0013] X a1 , X a2 and X a3 Each is N or CR a ;

[0014] X b1 , X b2 and X b3 Each is N or CR b ;

[0015] X c1 , X c2 and X c3 Each is N or CR c ;

[0016] Z a , Z b and Z c Independently selected from the group consisting of: single bond, NR N , O, C(O), BR B , S or no key; condition is Z a , Z b and Z c No more than two of them indicate no key;

[0017] R a , R b and R c Each represents a single substitution to the maximum number of substitutions allowed, or no substitution;

[0018] One, two or three occurrences of R N , R B , R a , R b and R c represents a bond to a metal M selected from the group consisting of Ir, Pt, Pd, Ru, Cu, Ag and Au;

[0019] M is further coordinated with one or more neutral ligands L or anionic ligands L' to satisfy the valence of M, provided that the metal complex of formula I is neutral;

[0020] R does not represent a bond to the metal M N , R B , R a , R b and R cis independently at each occurrence hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, nitrile, isonitrile, thiol, borane, acyl, carboxylic acid, ether, ester, sulfinyl, sulfonyl, cyano, phosphino, and combinations thereof; and

[0021] wherein any two adjacent substituents are optionally joined or fused together to form an optionally substituted ring.

[0022] In another aspect, the present disclosure provides a metal complex represented by Formula VII:

[0023]

[0024]

[0025] Ring A is a multi-ring structure capable of producing thermally activated delayed fluorescence;

[0026] each M is independently a metal selected from the group consisting of Au, Ag and Cu;

[0027] Each [carbene] independently represents a carbene ligand;

[0028] n is an integer having a value from 1 to 6;

[0029] wherein the compound is neutral;

[0030] Ring A has a singlet excitation energy S1 centered on the first ligand LC and the triplet excitation energy T1 centered on the first ligand LC ;

[0031] Where M has the first charge transfer excited state S1 CT and the first charge transfer triplet excited state T1 CT ;and

[0032] Among them, T1 CT and S1 LC The energy difference between them is ≤200meV.

[0033] In another aspect, the present disclosure provides a formulation comprising a metal complex of Formula I or Formula VII as described herein.

[0034] In yet another aspect, the present disclosure provides an OLED having an organic layer comprising the metal complex of Formula I or Formula VII described herein.

[0035] In yet another aspect, the present disclosure provides a consumer product comprising an OLED having an organic layer comprising the metal complex of Formula I or Formula VII described herein. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Figure 1 An organic light emitting device is shown.

[0037] Figure 2 An inverted organic light-emitting device without a separate electron transport layer is shown.

[0038] Figure 3 Exemplary structures of MR-TADF compounds are provided.

[0039] Figure 4 Illustrative examples of amide donors for converting aryl amines to CMA complexes are provided.

[0040] Figure 5 Exemplary structures of MR-TADF donor Type I complexes are provided.

[0041] Figure 6 Exemplary structures of MR-TADF donor Type II complexes are provided.

[0042] Figure 7 Exemplary structures of MR-TADF donor Type IV complexes are provided.

[0043] Figure 8 The results of natural transition orbital (NTO) calculations for Bim-based MR-TADF 4-1 are presented.

[0044] Fig. 9 The results of NTO calculations for the mononuclear CMA complex based on MR-TADF 1-1 are provided.

[0045] Fig.10 The results of NTO calculations for the binuclear CMA complex based on MR-TADF 1-1 are presented.

[0046] Fig.11 is a graph of the absorbance and emission of MACAuAzaB in different solvents.

[0047] Fig.12 Describe the relationship between inter-ligand charge transfer (ICT) and ligand center (LC) states in emissive compounds.

[0048] Fig.13 is a diagram of a computational screening of excited state energies of different carbenes on BN. Also shown are exemplary complexes BZAC-Au-BN (left) and PZI-Au-BN (right).

[0049] Fig.14 UV-Vis and photoluminescence of BZAC-Au-BN in different media: methylcyclohexane (MeCyHx), toluene, and dichloromethane (DCM).

[0050] Fig.15 are UV-Vis and photoluminescence images of PZI-Au-BN in different media: methylcyclohexane (MeCyHx), toluene, and 2-methyltetrahydrofuran (MeTHF). DETAILED DESCRIPTION

[0051] A. Terminology

[0052] Unless otherwise stated, the following terms used herein are defined as follows:

[0053] As used herein, the term "organic" includes polymeric materials and small molecule organic materials that can be used to make organic optoelectronic devices. "Small molecule" refers to any organic material that is not a polymer, and a "small molecule" may actually be quite large. In some cases, a small molecule may include a repeating unit. For example, the use of a long chain alkyl group as a substituent does not remove the molecule from the "small molecule" category. Small molecules can also be incorporated into polymers, for example as side groups on a polymer backbone or as part of a backbone. Small molecules can also serve as a dendritic core portion, which consists of a series of chemical shells built on the core portion. The dendritic core portion can be a fluorescent or phosphorescent small molecule emitter. Dendritic polymers can be "small molecules", and it is believed that all dendritic polymers currently used in the field of OLEDs are small molecules.

[0054] 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.

[0055] As used herein, "solution processable" means capable of being dissolved, dispersed or transported in and / or deposited from a liquid medium, either in solution or suspension form.

[0056] When the ligand is believed to directly contribute to the photosensitive properties of the emissive material, the ligand may be referred to as "photosensitive." When the ligand is believed not to contribute to the photosensitive properties of the emissive material, the ligand may be referred to as "ancillary," but the ancillary ligand may alter the properties of the photosensitive ligand.

[0057] 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.

[0058] 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.

[0059] The terms "halo," "halogen," and "halide" are used interchangeably and refer to fluorine, chlorine, bromine, and iodine.

[0060] The term "acyl" refers to a substituted carbonyl (C(O)-R s ).

[0061] The term "ester" refers to a substituted oxycarbonyl (-OC(O)-R s OR-C(O)-OR s ) group.

[0062] The term "ether" refers to -OR s Group.

[0063] The terms "thio" or "thioether" are used interchangeably and refer to -SR s Group.

[0064] The term "selenoalkyl" refers to -SeR s Group.

[0065] The term "sulfinyl" refers to -S(O)-R sGroup.

[0066] The term "sulfonyl" refers to -SO 2 -R s Group.

[0067] The term "phosphino" refers to -P(R s ) 3 A group, wherein each R s Can be the same or different.

[0068] The term "silyl" refers to -Si(R s ) 3 A group, wherein each R s Can be the same or different.

[0069] The term "germanyl" refers to -Ge(R s ) 3 A group, wherein each R s Can be the same or different.

[0070] The term "boryl" refers to -B(R s ) 2 The group or its Lewis adduct -B(R s ) 3 Group, where R s Can be the same or different.

[0071] In each of the above, R s R may be hydrogen or a substituent 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. s Selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0072] The term "alkyl" refers to and includes straight and branched chain alkyl groups. Preferred alkyl groups are those containing one to fifteen carbon atoms and include methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, etc. In addition, the alkyl group may be optionally substituted.

[0073] The term "cycloalkyl" refers to and includes monocyclic, polycyclic and spiroalkyl groups. 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, etc. In addition, the cycloalkyl group may be optionally substituted.

[0074] The term "heteroalkyl" or "heterocycloalkyl" refers to an alkyl or cycloalkyl group in which at least one carbon atom is replaced by a heteroatom, respectively. Optionally, at least one heteroatom is selected from O, S, N, P, B, Si and Se, preferably O, S or N. In addition, the heteroalkyl or heterocycloalkyl group may be optionally substituted.

[0075] The term "alkenyl" refers to and includes straight and branched alkenyl groups. Alkenyl groups are essentially alkyl groups that include at least one carbon-carbon double bond in the alkyl chain. Cycloalkenyl groups are essentially cycloalkyl groups that include at least one carbon-carbon double bond in the cycloalkyl ring. As used herein, the term "heteroalkenyl" refers to an alkenyl group in which at least one carbon atom is replaced by a heteroatom. Optionally, at least one heteroatom is selected from O, S, N, P, B, Si and Se, preferably O, S or N. Preferred alkenyl, cycloalkenyl or heteroalkenyl groups are those groups containing two to fifteen carbon atoms. In addition, alkenyl, cycloalkenyl or heteroalkenyl groups may be optionally substituted.

[0076] The term "alkynyl" refers to and includes straight and branched chain alkynyl groups. Alkynyl groups are essentially alkyl groups that include at least one carbon-carbon triple bond in the alkyl chain. Preferably, the alkynyl group is an alkynyl group containing two to fifteen carbon atoms. In addition, the alkynyl group may be optionally substituted.

[0077] The terms "aralkyl" or "arylalkyl" are used interchangeably and refer to an alkyl group substituted with an aryl group. Additionally, the aralkyl group may be optionally substituted.

[0078] 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, N, P, B, Si and Se, preferably O, S or N. Heteroaromatic cyclic groups can be used interchangeably with heteroaryl. Preferably, hetero non-aromatic cyclic groups are groups containing 3 to 7 ring atoms including at least one heteroatom, and include cyclic amines, such as morpholino, piperidino, pyrrolidino, etc., and cyclic ethers / thioethers, such as tetrahydrofuran, tetrahydropyran, tetrahydrothiophene, etc. In addition, heterocyclic groups can be optionally substituted.

[0079] The term "aryl" refers to and includes monocyclic aromatic hydrocarbons and polycyclic aromatic ring systems. Polycyclics may have two or more rings in which two carbons are shared by two adjacent rings (the rings are "fused"), wherein at least one ring is an aromatic hydrocarbon, for example, the other rings may be cycloalkyl, cycloalkenyl, aryl, heterocycle and / or heteroaryl. Preferably, the aryl is an aryl containing six to thirty carbon atoms, preferably six to twenty carbon atoms, more preferably six to twelve carbon atoms. Particularly preferred are aryls with six carbons, ten carbons or twelve carbons. Suitable aryls include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenanthren, phenanthrene, fluorene, pyrene, lettuce, perylene and azulene, preferably phenyl, biphenyl, terphenyl, triphenylene, fluorene and naphthalene. In addition, the aryl may be optionally substituted.

[0080] 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, N, P, B, Si and Se. In many cases, O, S or N are preferred heteroatoms. Monocyclic heteroaromatic systems are preferably monocyclic rings with 5 or 6 ring atoms, and the rings may have one to six heteroatoms. Heteropolycyclic ring systems may have two or more rings in which two carbons are shared by two adjacent rings (the rings are "fused"), wherein at least one ring is a heteroaryl, for example, the other rings may be cycloalkyl, cycloalkenyl, aryl, heterocycle and / or heteroaryl. Heteropolycyclic aromatic ring systems may have one to six heteroatoms in each ring of the polycyclic aromatic ring system. Preferably, the heteroaryl is a heteroaryl containing three to thirty carbon atoms, preferably three to twenty 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, 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, quinol In some embodiments, the heteroaryl group is substituted with 1,2-dibenzothiophene, 1,3-dibenzothiophene, 1,4 ...

[0081] Among the aryl and heteroaryl groups listed above, triphenylene, naphthalene, anthracene, dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, pyrazine, pyrimidine, triazine and benzimidazole groups and their respective corresponding aza analogs are of particular interest.

[0082] As used herein, the terms alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aralkyl, heterocyclyl, aryl and heteroaryl are independently unsubstituted or substituted with one or more common substituents.

[0083] 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.

[0084] 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.

[0085] In some cases, more preferred universal substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, alkoxy, aryloxy, amino, silanyl, aryl, heteroaryl, thio, and combinations thereof.

[0086] In still other cases, the most preferred universal substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0087] 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 available for the valence of a ring atom (such as a carbon atom in benzene and a nitrogen atom in pyrrole), or simply none for a fully valenced ring atom (such as a nitrogen atom in pyridine). The maximum number of substitutions possible in a ring structure will depend on the total number of available valences in the ring atoms.

[0088] 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.

[0089] 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.

[0090] 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. (Comments) 2007, 46, 7744-65, which are incorporated herein by reference in their entirety, which describe the deuteration of methylene hydrogens in benzylamines and the efficient pathways for replacing aromatic ring hydrogens with deuterium, respectively.

[0091] 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.

[0092] In some cases, a pair of adjacent substituents may be optionally joined or fused to form a ring. Preferred rings are five-membered, six-membered or seven-membered carbocyclic or heterocyclic rings, including two cases where a portion of the ring formed by the substituent pair is saturated and a portion of the ring formed by the substituent pair is unsaturated. As used herein, "adjacent" means that the two substituents involved may be immediately adjacent to each other on the same ring, or on two adjacent rings with two closest available substitutable positions (such as the 2,2' position in biphenyl or the 1,8 position in naphthalene), as long as they can form a stable fused ring system.

[0093] B. Compounds of the Disclosure

[0094] In one aspect, the present disclosure provides a metal complex of Formula I:

[0095]

[0096] in

[0097] Y is N or B;

[0098] X a1 , X a2 and X a3 Each is N or CR a ;

[0099] X b1 , X b2 and X b3 Each is N or CR b ;

[0100] X c1 , X c2 and X c3 Each is N or CR c ;

[0101] Z a , Z b and Z c Independently selected from the group consisting of: single bond, NR N , O, C(O), BR B , S or no key; condition is Z a , Z b and Z c No more than two of them indicate no key;

[0102] R a , R b and R c Each represents a single substitution to the maximum number of substitutions allowed, or no substitution;

[0103] One, two or three occurrences of R N , R B, R a , R b and R c represents a bond to a metal M selected from the group consisting of Ir, Pt, Pd, Ru, Cu, Ag and Au;

[0104] M is further coordinated with one or more neutral ligands L or anionic ligands L' to satisfy the valence of M, provided that the metal complex of formula I is neutral;

[0105] R does not represent a bond to the metal M N , R B , R a , R b and R c is independently at each occurrence hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, nitrile, isonitrile, thiol, borane, acyl, carboxylic acid, ether, ester, sulfinyl, sulfonyl, cyano, phosphino, and combinations thereof; and

[0106] wherein any two adjacent substituents are optionally joined or fused together to form an optionally substituted ring.

[0107] In one embodiment, the complex has the structure of Formula II:

[0108]

[0109] in

[0110] Z b ' is N or B;

[0111] Q 1 and Q 2 each independently represents CR, CRR', O, NR, N, S, Se, Br, BRR', SiRR', 1,2-arylene or 1,2-heteroarylene;

[0112] The condition is that when Q 2 When Q represents 1,2-phenylene, 1 does not represent CRR'; and when Q 1 When Q represents 1,2-phenylene, 2 It does not indicate CRR';

[0113] Each R and R' is independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, nitrile, isonitrile, thiol, borane, acyl, carboxylic acid, ether, ester, sulfinyl, sulfonyl, cyano, phosphino, and combinations thereof.

[0114] In one embodiment, Q 1 and Q 2 are fused together to form a benzene, pyridine, pyrimidine or pyrazine ring. In one embodiment, Q 1 and Q 2 Not fused together to form a benzene ring.

[0115] In one embodiment, Z a , Z b and Z c At least one of them independently represents Y' and together with the adjacent phenylene ring forms a group of formula A:

[0116]

[0117] in

[0118] Y' is N or B;

[0119] R A indicates a single substitution up to the maximum number of substitutions allowed, or no substitution; and

[0120] Each R A are independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, nitrile, isonitrile, thiol, borane, acyl, carboxylic acid, ether, ester, sulfinyl, sulfonyl, cyano, phosphino, and combinations thereof.

[0121] In one embodiment, Y is B. In one embodiment, Y is N.

[0122] In one embodiment, the metal complex is represented by Formula III:

[0123]

[0124] in:

[0125] Z d , Z e and Z f Independently selected from the group consisting of: single bond, NR N , O, C(O), BR B , S and keyless;

[0126] X d1 , X d2 and X d3 Each independently is N or CR d ;

[0127] X e1 , X e2 and X e3 Each independently is N or CR e ;

[0128] One, two or three occurrences of R N , R B , R a , R b , R c , R d and R e represents a bond to the metal M;

[0129] Each R not representing a bond to the metal M N , R B , R a , R b , R c , R d and R e are independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, nitrile, isonitrile, thiol, borane, acyl, carboxylic acid, ether, ester, sulfinyl, sulfonyl, cyano, phosphino, and combinations thereof; and

[0130] wherein any two adjacent substituents are optionally joined or fused together to form an optionally substituted ring.

[0131] In one embodiment, the metal complex is represented by Formula IIIa:

[0132]

[0133] X d1 , X d2 and X d3 Each is N or CR d ;

[0134] X e1 , X e2 and X e3 Each is N or CR e ;

[0135] One, two or three occurrences of R a , Rc , R d and R e represents a bond to the metal M;

[0136] Each R not representing a bond to the metal M d and R e are independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, nitrile, isonitrile, thiol, borane, acyl, carboxylic acid, ether, ester, sulfinyl, sulfonyl, cyano, phosphino, and combinations thereof;

[0137] wherein any two adjacent substituents are optionally joined or fused together to form an optionally substituted ring.

[0138] In one embodiment, the metal complex is represented by Formula IV:

[0139]

[0140] in:

[0141] Z a ' and Z b ' is independently present or absent, and if present, independently represents B or N;

[0142] Z d , Z e , Z f and Z g Independently selected from the group consisting of: single bond, NR N , O, C(O), BR B , S and keyless;

[0143] X d1 , X d2 and X d3 Each independently is N or CR d ;

[0144] X e1 , X e2 and X e3 Each independently is N or CR e ;

[0145] One, two or three occurrences of R N , R B , R a , R b , R c , R d and R e represents a bond to the metal M;

[0146] Each R not representing a bond to the metal M N , R B , R a , R b , R c , R d and R e are independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, nitrile, isonitrile, thiol, borane, acyl, carboxylic acid, ether, ester, sulfinyl, sulfonyl, cyano, phosphino, and combinations thereof; and

[0147] wherein any two adjacent substituents are optionally joined or fused together to form an optionally substituted ring.

[0148] In one embodiment, the metal complex is represented by Formula V:

[0149]

[0150] Z a ' and Z b ' is independently present or absent, and if present, independently represents B or N;

[0151] Y' and Y" are independently B or N;

[0152] Z d , Z e , Z f and Z g Independently selected from the group consisting of: single bond, NR N , O, C(O), BR B , S and keyless;

[0153] X d1 , X d2 and X d3 Each independently is N or CR d ;

[0154] X e1 , X e2 and X e3 Each independently is N or CR e ;

[0155] X f1 , X f2 and X f3 Each independently is N or CR f ;

[0156] Xg1 , X g2 and X g3 Each independently is N or CR g ;

[0157] One, two or three occurrences of R N , R B , R a , R b , R c , R d , R e , R f or R g represents a bond to the metal M;

[0158] Each R not representing a bond to the metal M N , R B , 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 deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, nitrile, isonitrile, thiol, borane, acyl, carboxylic acid, ether, ester, sulfinyl, sulfonyl, cyano, phosphino, and combinations thereof; and

[0159] wherein any two adjacent substituents are optionally joined or fused together to form an optionally substituted ring.

[0160] In one embodiment, the metal complex is represented by Formula VI:

[0161]

[0162] Z c 'Exists or does not exist, and if present, it means B or N;

[0163] Y' is B or N;

[0164] Z d and Z e Independently selected from the group consisting of: single bond, NR N , O, C(O), BR B , S and keyless;

[0165] X d1 , X d2 and X d3 Each independently is N or CR d ;

[0166] X e1 , X e2 and X e3 Each independently is N or CR e ;

[0167] One, two or three occurrences of R N , R B , R a , R b , R c , R d or R e represents a bond to the metal M;

[0168] Each R not representing a bond to the metal M N , R B , R a , R b , R c , R d and R e are independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, nitrile, isonitrile, thiol, borane, acyl, carboxylic acid, ether, ester, sulfinyl, sulfonyl, cyano, phosphino, and combinations thereof; and

[0169] wherein any two adjacent substituents are optionally joined or fused together to form an optionally substituted ring.

[0170] In one embodiment, the metal complex is represented by one of the following structures:

[0171]

[0172]

[0173] In one embodiment, each metal M is monovalent and each metal M is independently bound to a neutral carbene ligand L.

[0174] In one embodiment, each neutral carbene ligand L is independently selected from the group consisting of: Formula B, Formula C, Formula D, Formula E, Formula F, and Formula G:

[0175]

[0176] in

[0177] X 1 To X 4 Each independently represents NR 1 , CR 1R 2 , C=O, C=S, O or S; and

[0178] R 1 and R 2 is independently selected at each occurrence from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, nitrile, isonitrile, thiol, borane, acyl, carboxylic acid, ether, ester, sulfinyl, sulfonyl, cyano, phosphino, and combinations thereof;

[0179] Any two adjacent R 1 and R 2 are optionally joined or fused together to form an optionally substituted ring.

[0180]

[0181] Each X 1 and X 4 Independently represent N, NR 1 , CR 1 , CR 1 R 2 、SiR 1 、SiR 1 R 2 , PR 1 , B, BR 1 , BR 1 R 2 , O or S; and

[0182] Each X 2 and X 3 Independently express CR 1 , CR 1 R 2 、SiR 1 、SiR 1 R 2 , N, NR 1 ,P,PR 1 , B, BR 1 , O or S;

[0183] R 1 and R 2 is independently at each occurrence hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, nitrile, isonitrile, thiol, borane, acyl, carboxylic acid, ether, ester, sulfinyl, sulfonyl, cyano, phosphino, and combinations thereof;

[0184] Any two adjacent R 1 and R 2 are optionally joined or fused together to form an optionally substituted ring; and

[0185] Dashed lines within the five-membered ring represent zero or one double bonds.

[0186]

[0187] Where X 1 and X 2 Each independently represents NR 1 , CR 1 R 2 , O or S;

[0188] R 1 and R 2 is independently at each occurrence hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, nitrile, isonitrile, thiol, borane, acyl, carboxylic acid, ether, ester, sulfinyl, sulfonyl, cyano, phosphino, and combinations thereof; and

[0189] Any two adjacent R 1 and R 2 are optionally joined or fused together to form an optionally substituted ring.

[0190]

[0191] in

[0192] Each X 1 To X 5 Independently represent N, P, NR 1 , PR 1 , B, BR 1 , CR 1 、SiR 1 , CR 1 R 2 、SiR 1 R 2 , C=O, C=S, O or S;

[0193] n is 0 or 1;

[0194] R 1 and R 2is independently at each occurrence hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, nitrile, isonitrile, thiol, borane, acyl, carboxylic acid, ether, ester, sulfinyl, sulfonyl, cyano, phosphino, and combinations thereof;

[0195] Any two adjacent R 1 and R 2 are optionally joined or fused together to form an optionally substituted ring;

[0196]

[0197] in

[0198] Each X 1 and X 4 Independently represents NR 1 , CR 1 、SiR 1 , CR 1 R 2 、SiR 1 R 2 , PR 1 , BR 1 , C=O, C=S, O or S;

[0199] Each X 2 and X 3 is independently present or absent, and if present, independently represents H, NR 1 R 2 , CR 1 , CR 1 R 2 , C=O, C=S, O or S;

[0200] R 1 and R 2 is independently at each occurrence hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, nitrile, isonitrile, thiol, borane, acyl, carboxylic acid, ether, ester, sulfinyl, sulfonyl, cyano, phosphino, and combinations thereof;

[0201] Any two adjacent R 1 and R 2 are optionally joined or fused together to form an optionally substituted ring

[0202]

[0203] Where X 1 To X 8 Indicates N, P, NR independently at each occurrence 1 , PR 1 , B, BR 1 , CR 1 、SiR 1 , CR 1 R 2 、SiR 1 R 2 , C=O, C=S, O or S;

[0204] n is 1 or 2;

[0205] R 1 and R 2 is independently at each occurrence hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, nitrile, isonitrile, thiol, borane, acyl, carboxylic acid, ether, ester, sulfinyl, sulfonyl, cyano, phosphino, and combinations thereof;

[0206] Any two adjacent R 1 and R 2 are optionally joined or fused together to form an optionally substituted ring.

[0207] In one embodiment, each neutral carbene ligand L is independently represented by one of the following structures:

[0208]

[0209]

[0210]

[0211] wherein each R is independently selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, amide, hydroxy, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, heteroalkynyl, aryl, heteroaryl, nitro, nitrile, isonitrile, thiol, borane, acyl, carboxylic acid, benzoyl, ether, ester, vinyl, ketone, sulfinyl, sulfonyl, cyano, phosphino, and combinations thereof; wherein two adjacent substituents may be joined together to form a ring.

[0212] In one embodiment, each neutral carbene ligand L is independently represented by one of the following structures:

[0213]

[0214] Among them, each R1 , R 2 and R 3 independently selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, amide, hydroxy, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, heteroalkynyl, aryl, heteroaryl, nitro, nitrile, isonitrile, thiol, borane, acyl, carboxylic acid, benzoyl, ether, ester, vinyl, ketone, sulfinyl, sulfonyl, cyano, phosphino, and combinations thereof; wherein two adjacent substituents may be joined together to form a heteroaryl ring, an aromatic ring, a cycloalkyl ring, or a bicyclic ring; and

[0215] wherein each Ar independently represents an aryl or heteroaryl group, which is optionally further substituted with one or more substituents independently selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, amide, hydroxy, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, heteroalkynyl, aryl, heteroaryl, nitro, nitrile, isonitrile, thiol, borane, acyl, carboxylic acid, benzoyl, ether, ester, vinyl, ketone, sulfinyl, sulfonyl, cyano, phosphino, and combinations thereof; wherein any two adjacent substituents may be joined together to form a ring.

[0216] In one embodiment, each neutral carbene ligand L is independently represented by one of the following structures:

[0217]

[0218] Where dipp = 2,6-diisopropylphenyl.

[0219] In one aspect, the present disclosure relates to a metal complex represented by Formula VII:

[0220]

[0221] Ring A is a multi-ring structure capable of producing thermally activated delayed fluorescence;

[0222] each M is independently a metal selected from the group consisting of Au, Ag and Cu;

[0223] Each [carbene] independently represents a carbene ligand;

[0224] n is an integer having a value from 1 to 6;

[0225] wherein the compound is neutral;

[0226] Ring A has a singlet excitation energy S1 centered on the first ligand LC and the triplet excitation energy T1 centered on the first ligand LC ;

[0227] Where M has the first charge transfer excited state S1 CT and the first charge transfer triplet excited state T1 CT ;and

[0228] Among them, T1 CT and S1 LC The energy difference between them is ≤200meV.

[0229] In one embodiment, T1 CT With S1 LC The energy difference between them is ≤175meV. In one embodiment, T1 CT With S1 LC The energy difference between them is ≤150meV. In one embodiment, T1 CT With S1 LC The energy difference between them is ≤125meV. In one embodiment, T1 CT With S1 LC The energy difference between them is ≤100meV. In one embodiment, T1 CT With S1 LC The energy difference between them is ≤75meV. In one embodiment, T1 CT With S1 LC The energy difference between them is ≤50meV.

[0230] In one embodiment, ring A is any polycyclic structure known to produce thermally activated delayed fluorescence. In one embodiment, ring A has a structure of any one of formula I, II, III, IIIA, IV, V, VI, or any other embodiment or structure presented herein. In one embodiment, M is covalently bonded to an atom on ring A selected from the group consisting of carbon, boron, and nitrogen.

[0231] In some embodiments, the metal complexes of Formula I described herein can be at least 30% deuterated, at least 40% deuterated, at least 50% deuterated, at least 60% deuterated, at least 70% deuterated, at least 80% deuterated, at least 90% deuterated, at least 95% deuterated, at least 99% deuterated, or 100% deuterated. As used herein, percent deuteration has its ordinary meaning and includes the percentage of possible hydrogen atoms (e.g., positions that are hydrogen or deuterium) that are replaced by deuterium atoms.

[0232] C. OLEDs and Devices of the Present Disclosure

[0233] 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.

[0234] In some embodiments, an OLED comprises: an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises a metal complex of Formula I:

[0235]

[0236] in

[0237] Y is N or B;

[0238] X a1 , X a2 and X a3 Each is N or CR a ;

[0239] X b1 , X b2 and X b3 Each is N or CR b ;

[0240] X c1 , X c2 and X c3 Each is N or CR c ;

[0241] Z a , Z b and Z c Independently selected from the group consisting of: single bond, NR N , O, C(O), BR B , S or no key; condition is Z a , Z b and Z c No more than two of them indicate no key;

[0242] R a , R b and R c Each represents a single substitution to the maximum number of substitutions allowed, or no substitution;

[0243] One, two or three occurrences of R N , R B , R a , R b and R c represents a bond to a metal M selected from the group consisting of Ir, Pt, Pd, Ru, Cu, Ag and Au;

[0244] M is further coordinated with one or more neutral ligands L or anionic ligands L' to satisfy the valence of M, provided that the metal complex of formula I is neutral;

[0245] R does not represent a bond to the metal M N , RB , R a , R b and R c is independently at each occurrence hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, nitrile, isonitrile, thiol, borane, acyl, carboxylic acid, ether, ester, sulfinyl, sulfonyl, cyano, phosphino, and combinations thereof; and

[0246] wherein any two adjacent substituents are optionally joined or fused together to form an optionally substituted ring.

[0247] In some embodiments, an OLED comprises: an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises a metal complex represented by Formula VII:

[0248]

[0249] Ring A is a multi-ring structure capable of producing thermally activated delayed fluorescence;

[0250] each M is independently a metal selected from the group consisting of Au, Ag and Cu;

[0251] Each [carbene] independently represents a carbene ligand;

[0252] n is an integer having a value from 1 to 6;

[0253] wherein the compound is neutral;

[0254] Ring A has a singlet excitation energy S1 centered on the first ligand LC and the triplet excitation energy T1 centered on the first ligand LC ;

[0255] Where M has the first charge transfer excited state S1 CT and the first charge transfer triplet excited state T1 CT ;and

[0256] Among them, T1 CT and S1 LC The energy difference between them is ≤200meV.

[0257] 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.

[0258] In some embodiments, the emissive layer comprises one or more quantum dots.

[0259] In some embodiments, the organic layer may further comprise a host, wherein the host comprises a triphenylene containing a benzo-fused thiophene or a benzo-fused furan, wherein any substituent in the host is a non-fused substituent independently selected from the group consisting of: C n H 2n+1 , OC n H 2n+1 ,OAr 1 、N(C n H 2n+1 ) 2 、N(Ar 1 )(Ar 2 ), CH=CH-C n H 2n+1 、C≡CC n H 2n+1 ,Ar 1 ,Ar 1 -Ar 2 , C n H 2n -Ar 1 or unsubstituted, wherein n is an integer from 1 to 10; and wherein Ar 1 and Ar 2 Independently selected from the group consisting of benzene, biphenyl, naphthalene, triphenylene, carbazole, and heteroaromatic analogs thereof.

[0260] 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, 5λ2-benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, 5,9-dioxa-13b-borazinonaphtho[3,2,1-de]anthracene, triazine, borane, silane, aza-triphenylene, aza-carbazole, aza-indolecarbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, aza-5λ2-benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, and aza-(5,9-dioxa-13b-borazinonaphtho[3,2,1-de]anthracene).

[0261] In some embodiments, the subject can be selected from the group of subjects consisting of:

[0262]

[0263]

[0264] and combinations thereof.

[0265] In some embodiments, the organic layer may further include a host, wherein the host includes a metal complex.

[0266] In some embodiments, the emissive layer may include two hosts: a first host and a second host. In some embodiments, the first host is a hole transport host and the second host is an electron transport host. In some embodiments, the first host and the second host may form an exciplex.

[0267] In some embodiments, a compound as described herein may be a sensitizer; wherein the device may further comprise a receptor; and wherein the receptor may be selected from the group consisting of: a fluorescent emitter, a delayed fluorescent emitter, and combinations thereof.

[0268] In yet another aspect, the OLED of the present disclosure may further comprise an emissive region comprising a compound as disclosed in the above compound section of the present disclosure.

[0269] In some embodiments, the emissive region may comprise a metal complex of Formula I:

[0270]

[0271] in

[0272] Y is N or B;

[0273] X a1 , X a2 and X a3 Each is N or CR a ;

[0274] X b1 , X b2 and X b3 Each is N or CR b ;

[0275] X c1 , X c2 and X c3 Each is N or CR c ;

[0276] Z a , Z b and Z c Independently selected from the group consisting of: single bond, NR N , O, C(O), BR B , S or no key; condition is Z a , Z b and Z c No more than two of them indicate no key;

[0277] R a , R band R c Each represents a single substitution to the maximum number of substitutions allowed, or no substitution;

[0278] One, two or three occurrences of R N , R B , R a , R b and R c represents a bond to a metal M selected from the group consisting of Ir, Pt, Pd, Ru, Cu, Ag and Au;

[0279] M is further coordinated with one or more neutral ligands L or anionic ligands L' to satisfy the valence of M, provided that the metal complex of formula I is neutral;

[0280] R does not represent a bond to the metal M N , R B , R a , R b and R c is independently at each occurrence hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, nitrile, isonitrile, thiol, borane, acyl, carboxylic acid, ether, ester, sulfinyl, sulfonyl, cyano, phosphino, and combinations thereof; and

[0281] wherein any two adjacent substituents are optionally joined or fused together to form an optionally substituted ring.

[0282] In some embodiments, the emissive region may comprise a metal complex of Formula VII:

[0283]

[0284] Ring A is a multi-ring structure capable of producing thermally activated delayed fluorescence;

[0285] each M is independently a metal selected from the group consisting of Au, Ag and Cu;

[0286] Each [carbene] independently represents a carbene ligand;

[0287] n is an integer having a value from 1 to 6;

[0288] wherein the compound is neutral;

[0289] Ring A has a singlet excitation energy S1 centered on the first ligand LC and the triplet excitation energy T1 centered on the first ligand LC ;

[0290] Where M has the first charge transfer excited state S1 CT and the first charge transfer triplet excited state T1 CT ;and

[0291] Among them, T1 CT and S1 LC The energy difference between them is ≤200meV.

[0292] In some embodiments, at least one of the anode, cathode, or new layer disposed above the organic emission layer acts as an enhancement layer. The enhancement layer includes a plasmon material that exhibits 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. The enhancement layer is disposed at a distance from the organic emission layer that does not exceed a threshold distance, wherein due to the presence of the enhancement layer, the emitter material has a total non-radiative decay rate constant and a total radiative decay rate constant, and the threshold distance is the position where the total non-radiative decay rate constant is equal to the total radiative decay rate constant. In some embodiments, the OLED further includes an outcoupling layer. In some embodiments, the outcoupling layer is disposed above the enhancement layer on the opposite side of the organic emission layer. In some embodiments, the outcoupling layer is disposed on the opposite side of the emission layer from the enhancement layer, but still couples energy from the surface plasmon mode of the enhancement layer. The outcoupling layer scatters energy from the 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 modes of the device into other modes, such as but not limited to organic waveguide modes, substrate modes, or another waveguide mode. If energy is scattered into non-free space modes of the OLED, other outcoupling schemes may be incorporated to extract the energy into free space. In some embodiments, one or more intermediate layers may be disposed between the enhancement layer and the outcoupling layer. Examples of intermediate layers may be dielectric materials, including organic, inorganic, perovskite, oxides, and may include stacks and / or mixtures of these materials.

[0293] 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, change in emission intensity versus angle, change in stability of the emitter material, change in 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 sides 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.

[0294] The enhancement layer may comprise a plasmonic material, an optically active metamaterial, or a hyperbolic metamaterial. As used herein, a plasmonic material is a material whose real part of the dielectric constant crosses zero in the visible or ultraviolet region of the electromagnetic spectrum. In some embodiments, the plasmonic material comprises at least one metal. In such embodiments, the metal may include at least one of the following: Ag, Al, Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ru, Pd, In, Bi, Ca, alloys or mixtures of these materials, and stacks of these materials. In general, a metamaterial is a medium composed of different materials, where the effect of the medium as a whole is different from the sum of its material parts. Specifically, we define an optically active metamaterial as a material that has both negative permittivity and negative permeability. On the other hand, a hyperbolic metamaterial is an anisotropic medium, where the permittivity or permeability has different signs for different spatial directions. Optically active metamaterials and hyperbolic metamaterials are strictly distinguished from many other photonic structures, such as distributed Bragg reflectors ("DBRs"), in that the medium should appear uniform in the direction of propagation on the length scale of the wavelength of light. Using terms that are understood by those skilled in the art: the dielectric constant of a metamaterial in the direction of propagation can be approximated by an effective medium. Plasmonic materials and metamaterials provide a way to control light propagation that can enhance OLED performance in a variety of ways.

[0295] 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. In some embodiments, the wavelength-scale features and sub-wavelength-scale features have sharp edges.

[0296] In some embodiments, the outcoupling layer has wavelength-sized features that are periodically, quasi-periodically, or randomly arranged, or has sub-wavelength-sized features that are periodically, quasi-periodically, or randomly arranged. In some embodiments, the outcoupling layer can be composed of a plurality of nanoparticles, and in other embodiments, the outcoupling layer is composed of a plurality of nanoparticles disposed above a material. In these embodiments, the outcoupling can be tuned by at least one of: changing the size of the plurality of nanoparticles, changing the shape of the plurality of nanoparticles, changing the material of the plurality of nanoparticles, adjusting the thickness of the material, changing the refractive index of the material or an additional layer disposed on the plurality of nanoparticles, changing the thickness of the enhancement layer, and / or changing the material of the enhancement layer. The plurality of nanoparticles of the device can be formed of at least one of: a metal, a dielectric material, a semiconductor material, 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 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, Ca, alloys or mixtures of these materials, and stacks of these materials. Multiple nanoparticles can have additional layers disposed on them. In some embodiments, the outcoupling layer can be used to adjust the polarization of the emission. Changing the size and periodicity of the outcoupling layer can select the polarization type that is preferentially outcoupled to air. In some embodiments, the outcoupling layer also acts as an electrode of the device.

[0297] On the other hand, the present disclosure also provides a consumer product comprising an organic light-emitting device (OLED), wherein the organic light-emitting device has an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer may contain a compound as disclosed in the above-mentioned compound section of the present disclosure.

[0298] In some embodiments, a consumer product comprises an OLED having an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer may comprise a metal complex of Formula I or a metal complex of Formula VII described herein.

[0299] In some embodiments, the consumer product can be one of the following: a flat panel display, a computer monitor, a medical monitor, a television, a sign, a light for interior or exterior lighting and / or signaling, a head-up display, a fully or partially transparent display, a flexible display, a laser printer, a phone, a cell phone, a tablet computer, a phablet, a personal digital assistant (PDA), a wearable device, a laptop computer, a digital camera, a camcorder, a viewfinder, a microdisplay with a diagonal of less than 2 inches, a 3-D display, a virtual reality or augmented reality display, a vehicle, a video wall comprising multiple displays tiled together, a theater or stadium screen, a light therapy device, and a sign.

[0300] 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, "excitons" are formed, which are localized electron-hole pairs with excited energy states. When the excitons relax via a photoemission mechanism, light is emitted. Excitons can be confined to excimers or excited complexes. Non-radiative mechanisms (such as thermal relaxation) may also occur, but are generally considered undesirable.

[0301] Several OLED materials and configurations are described in US Pat. Nos. 5,844,363, 6,303,238, and 5,707,745, which are incorporated herein by reference in their entirety.

[0302] The original OLEDs utilized emissive molecules to emit light from their singlet states ("fluorescence"), as disclosed, for example, in US Pat. No. 4,769,292, which is incorporated by reference in its entirety. Fluorescence emission typically occurs in a time frame of less than 10 nanoseconds.

[0303] Recently, OLEDs with emissive materials that emit light from triplet states ("phosphorescence") have been demonstrated. The following references are incorporated herein by reference in their entirety: Baldo et al., "Highly Efficient Phosphorescent Emission from Organic Electroluminescent Devices," Nature, Vol. 395, 151-154, 1998; ("Baldo-I") and Baldo et al., "Very high-efficiency green organic light-emitting devices based on electrophosphorescence," Appl. Phys. Lett., Vol. 75, Nos. 3, 4-6 (1999) ("Baldo-II"). Phosphorescence is described in more detail in U.S. Pat. No. 7,279,704, Col. 5-6, which is incorporated by reference.

[0304] FIG. Figure 1 An organic light emitting device 100 is shown. The figure is not necessarily drawn to scale. The device 100 may include a substrate 110, an anode 115, a hole injection layer 120, a hole transport layer 125, an electron blocking layer 130, an emission layer 135, a hole blocking layer 140, an electron transport layer 145, an electron injection layer 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 various layers and example materials are described in more detail in US 7,279,704, columns 6-10, which is incorporated by reference.

[0305] More examples of each of these layers are available. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. Patent No. 5,844,363, which is incorporated by reference in its entirety. An example of a p-doped hole transport layer is a 50:1 molar ratio of F doped 4-TCNQ m-MTDATA, as disclosed in U.S. Patent Application Publication No. 2003 / 0230980, which is incorporated by reference in its entirety. Examples of emissive and host materials are disclosed in U.S. Patent No. 6,303,238 to Thompson et al., which is incorporated by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li in a 1:1 molar ratio, as disclosed in U.S. Patent Application Publication No. 2003 / 0230980, which is incorporated by reference in its entirety. U.S. Patent Nos. 5,703,436 and 5,707,745 disclose examples of cathodes, including composite cathodes having a thin layer of metal (e.g., Mg:Ag) covered with a sputter-deposited transparent conductive ITO layer, which are incorporated by reference in their entirety. The theory and use of barrier layers are described in more detail in U.S. Patent No. 6,097,147 and U.S. Patent Application Publication No. 2003 / 0230980, which are incorporated herein by reference in their entirety. Examples of injection layers are provided in U.S. Patent Application Publication No. 2004 / 0174116, which is incorporated herein by reference in its entirety. A description of protective layers can be found in U.S. Patent Application Publication No. 2004 / 0174116, which is incorporated herein by reference in its entirety.

[0306] 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.

[0307] 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.

[0308] 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.

[0309] 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 performed in nitrogen or an inert atmosphere. For other layers, preferred methods include thermal evaporation. Preferred patterning methods include deposition through a mask, 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), and 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. Materials having asymmetric structures may have better solution processability than materials having symmetric structures 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.

[0310] The device manufactured according to the embodiment of the present disclosure may further optionally include a barrier layer. One purpose of the barrier layer is to protect the electrode and the organic layer from exposure to harmful substances in the environment including moisture, steam and / or gas, etc. The barrier layer can be deposited on the substrate, the electrode, under the substrate, the electrode, or beside the substrate, the electrode, or on any other part (including the edge) of the device. The barrier layer may include a single layer or multiple layers. The barrier layer can be formed by various known chemical vapor deposition techniques, and may include a composition with a single phase and a composition with multiple phases. Any suitable material or material combination can be used for the barrier layer. The barrier layer can be incorporated into an inorganic compound or an organic compound or both. The preferred barrier layer includes a mixture of a polymeric material and a non-polymeric material, as described in U.S. Patent No. 7,968,146, PCT Patent Application No. PCT / US2007 / 023098 and No. PCT / US2009 / 042829, which are incorporated herein by reference in their entirety. In order to be considered a "mixture", the aforementioned polymer and non-polymer materials constituting the barrier layer should be deposited under the same reaction conditions and / or deposited simultaneously. The weight ratio of the polymer material relative to the non-polymer material can be in the range of 95:5 to 5:95. The polymer material and the non-polymer material can be produced from the same precursor material. In one example, the mixture of the polymer material and the non-polymer material consists essentially of polymeric silicon and inorganic silicon.

[0311] Devices manufactured according to embodiments of the present disclosure may be incorporated into a variety of electronic component modules (or units), which may be incorporated into a variety of electronic products or intermediate components. Examples of such electronic products or intermediate components include display screens, lighting devices (e.g., discrete light source devices or lighting panels), etc., which may be utilized by end-user product manufacturers. Such electronic component modules may optionally include drive electronics and / or power supplies. Devices manufactured according to embodiments of the present disclosure may be incorporated into a variety of consumer products, which may include one or more electronic component modules (or units). A consumer product comprising an OLED is disclosed, wherein 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).

[0312] 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.

[0313] 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.

[0314] 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.

[0315] In some embodiments, the OLED further comprises a layer containing a delayed fluorescent emitter. 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.

[0316] In some embodiments, the compound may be an emitting dopant. In some embodiments, the compound may be emitted via phosphorescence, fluorescence, thermally activated delayed fluorescence (i.e., TADF, also referred to as E-type delayed fluorescence; see, for example, U.S. Application No. 15 / 700,352, which is incorporated herein by reference in its entirety), triplet-triplet annihilation, or a combination of these processes. In some embodiments, the emitting dopant may be a racemic mixture, or may be enriched in one enantiomer. In some embodiments, the compound may be homogeneous (each ligand is the same). In some embodiments, the compound may 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 may all be the same. In some other embodiments, at least one ligand is different from the other ligands. In some embodiments, each ligand may be different from each other. This is also true in 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).

[0317] In some embodiments, the compound can be used as a phosphorescent sensitizer in an OLED, wherein one or more layers in the OLED contain an acceptor in the form of one or more fluorescent and / or delayed fluorescent emitters. In some embodiments, the compound can be used as a component of an excitation 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 be in the range of 0.001% to 100%. 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 TADF emitter. In some embodiments, the acceptor is a fluorescent emitter. In some embodiments, the emission may be generated by any one or all of the sensitizer, the acceptor, and the final emitter.

[0318] According to another aspect, a formulation comprising a compound described herein is also disclosed.

[0319] The OLEDs disclosed herein may be incorporated into one or more consumer products, electronic component modules, and lighting panels.The organic layer may be an emissive layer, and the compound may be an emissive dopant in some embodiments, while the compound may be a non-emissive dopant in other embodiments.

[0320] 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, a host, a hole injection material, a hole transport material, an electron blocking material, a hole blocking material, and an electron transport material.

[0321] The present disclosure encompasses any chemical structure comprising the novel compounds of the present disclosure or their monovalent or multivalent variants. In other words, the compounds of the present invention or their monovalent or multivalent variants can be part of a larger chemical structure. Such chemical structures can be selected from the group consisting of: monomers, polymers, macromolecules and supramolecules (also referred to as supermolecules). As used herein, "monovalent variants of a compound" refers to the same portion as the compound, but one of the hydrogens has been removed and replaced with a bond to the rest of the chemical structure. As used herein, "multivalent variants of a compound" refers to the same portion as the compound, but more than one hydrogen has been removed and replaced with one or more bonds to the rest of the chemical structure. In the case of supramolecules, the compounds of the present invention can also be incorporated into supramolecular complexes without covalent bonds.

[0322] D. Combinations of Compounds of the Disclosure with Other Materials

[0323] The materials described herein as being useful for specific layers in an organic light-emitting device can be used in combination with a variety of other materials present in the device. For example, the light-emitting dopants disclosed herein can be used in combination with a variety of hosts, transport layers, barrier layers, injection layers, electrodes, and other layers that may be present. The materials described or mentioned below are non-limiting examples of materials that can be used in combination with the compounds disclosed herein, and those skilled in the art can easily consult the literature to identify other materials that can be used in combination.

[0324] a) Conductive dopants:

[0325] The charge transport layer can be doped with a conductivity 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.

[0326] Non-limiting examples of conductive dopants that can be used in OLEDs in combination with the materials disclosed herein are illustrated below and in the references that disclose those materials: EP01617493, EP01968131, EP2020694, EP2684932, US20050139810, US20070160905, US20090167167, US2010288362, WO06081780, WO2009003455, WO2009008277, WO2009011327, WO2014009310, US2007252140, US2015060804, US20150123047, and US2012146012.

[0327]

[0328]

[0329] b)HIL / HTL:

[0330] 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 conductive dopants; 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.

[0331] Examples of aromatic amine derivatives for use in HIL or HTL include, but are not limited to, the following general structure:

[0332]

[0333] Ar 1 To Ar 9Each 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, wherein the cyclic structural units are groups of the same type or different types selected from aromatic hydrocarbon ring groups and aromatic heterocyclic groups and are directly 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 Ar may be unsubstituted or may be substituted with a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof.

[0334] In one aspect, Ar 1 To Ar 9 Independently selected from the group consisting of:

[0335]

[0336] Wherein k is an integer from 1 to 20; X 101 To X 108 is C (including CH) or N; Z 101 It is NAr 1 , O or S; Ar 1 Having the same groups as defined above.

[0337] Examples of metal complexes used in HIL or HTL include, but are not limited to, the following general formula:

[0338]

[0339] Where Met is a metal with an atomic weight greater than 40; (Y 101 -Y 102 ) is a bidentate ligand, Y101 and Y 102 is independently selected from C, N, O, P and S; L 101 is an auxiliary 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.

[0340] In one aspect, (Y 101 -Y 102 ) is a 2-phenylpyridine derivative. On the other hand, (Y 101 -Y 102 ) is a carbene ligand. In another aspect, Met is selected from Ir, Pt, Os and Zn. In another aspect, the metal complex is in solution relative to Fc + The / Fc pair has a minimum oxidation potential of less than about 0.6V.

[0341] Non-limiting examples of HIL and HTL materials that can be used in OLEDs in combination with the materials disclosed herein are illustrated below, along with references disclosing those materials: CN102702075, DE102012005215, EP01624500, EP01698613, EP01806334, EP01930964, EP01972613, EP01997799, EP02011790, EP02055700, EP02055701, EP1725079, EP2085382, EP2660300, EP650955, JP07-073529, JP2005112765, JP2007091719, JP2008021687, JP2014-009196, KR20110088898, KR201300 77473, TW201139402, US06517957, US20020158242, US20030162053, US200 50123751, US20060182993, US20060240279, US20070145888, US200701818 74. US20070278938, US20080014464, US20080091025, US20080106190, US20 080124572, US20080145707, US20080220265, US20080233434, US20080303417, US2008107919, US20090115320, US20090167161, US2009066235, US20 11007385, US20110163302, US2011240968, US2011278551, US2012205642, US2013241401, US20140117329, US2014183517, US5061569, US5639914, WO0 5075451, WO07125714, WO08023550, WO08023759, WO2009145016, WO2010061824, WO2011075644, WO2012177006, WO2013018530, WO2013039073, WO201 3087142, WO2013118812, WO2013120577, WO2013157367, WO2013175747, WO 2014002873, WO2014015935, WO2014015937, WO2014030872, WO2014030921,WO2014034791, WO2014104514, WO2014157018. ,

[0342]

[0343]

[0344]

[0345]

[0346]

[0347]

[0348] c) EBL:

[0349] An electron blocking layer (EBL) can be used to reduce the number of electrons and / or excitons that leave the emissive layer. The presence of such a blocking layer in the device can result in significantly improved efficiency and / or longer lifetime compared to a similar device lacking a blocking layer. In addition, a blocking layer can be used to confine emission to 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 the emitter closest to the EBL interface. 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 hosts closest to the EBL interface. In one aspect, the compound used in the EBL contains the same molecule or the same functional group as used in one of the hosts described below.

[0350] d) Subject:

[0351] The light-emitting layer in the organic EL device of the present disclosure preferably contains at least one metal complex as a light-emitting material, and may contain a host material using the metal complex as a doping material. Examples of host materials are not particularly limited, and any metal complex or organic compound may be used as long as the triplet energy of the host is greater than the triplet energy of the dopant. Any host material may be used with any dopant as long as the triplet criterion is met.

[0352] Examples of metal complexes used as matrices preferably have the following general formula:

[0353]

[0354] Where Met is a metal; (Y 103 -Y 104 ) is a bidentate ligand, Y 103 and Y 104is independently selected from C, N, O, P and S; L 101 is another ligand; k' is an integer value from 1 to the maximum number of ligands that can be attached to the metal; and k'+k" is the maximum number of ligands that can be attached to the metal.

[0355] In one aspect, the metal complex is:

[0356]

[0357] wherein (ON) is a bidentate ligand having a metal coordinated to O and N atoms.

[0358] In another aspect, Met is selected from Ir and Pt. In another aspect, (Y 103 -Y 104 ) is a carbene ligand.

[0359] In one aspect, the host compound contains at least one of the following groups, the group consisting of aromatic hydrocarbon cyclic compounds, such as benzene, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenanthrene, phenanthrene, fluorene, pyrene, letrozole, perylene and azulene; the group consisting of aromatic heterocyclic compounds, such as 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, benzimidazole, indazole, indoloxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, 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, wherein the cyclic structural units are groups of the same type or different types selected from aromatic hydrocarbon ring groups and aromatic heterocyclic groups and are bonded to each other directly or via at least one of oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms, phosphorus atoms, boron atoms, chain structural units and aliphatic ring groups. Each option within each group may be unsubstituted or substituted with a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof.

[0360] In one aspect, the subject compound contains at least one of the following groups in the molecule:

[0361]

[0362]

[0363] Where R 101 is selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof; and when it is aryl or heteroaryl, it has a similar definition to that of Ar above. k is an integer from 0 to 20 or from 1 to 20. X 101 To X 108 Z is independently selected from C (including CH) or N. 101 and Z 102 Independently selected from NR 101 , O or S.

[0364] Non-limiting examples of host materials that can be used in OLEDs in combination with the materials disclosed herein are illustrated below, along with references disclosing those materials: EP2034538, EP2034538A, EP2757608, JP2007254297, KR20100079458, KR20120088644, KR20120129733, KR20130115564, TW201329200, US20030175553, US20050238919, US20060280965, US2008 090017330, US20090030202, US20090167162, US20090302743, US20090309488, US20100012931, US20100084966, US2010018798 4. US2010187984, US2012075273, US2012126221, US2013009543, US2013105787, US2013175519, US2014001446, US20140183503, US20140225088, US2014034914, US7154114, WO2001039234, WO2004093207, WO2005014551, WO2005089025, WO2006072002, WO20 06114966, WO2007063754, WO2008056746, WO2009003898, WO2009021126, WO2009063833, WO2009066778, WO2009066779, WO20090 86028, WO2010056066, WO2010107244, WO2011081423, WO2011081431, WO2011086863, WO2012128298, WO2012133644, WO2012133 649. WO2013024872, WO2013035275, WO2013081315, WO2013191404, WO2014142472, US20170263869, US20160163995, US9466803,

[0365]

[0366]

[0367]

[0368]

[0369]

[0370] e) Other emitters:

[0371] One or more other emitter dopants may be used in combination with the compounds of the present disclosure. Examples of other emitter dopants are not particularly limited, and any compound may be used as long as the compound is commonly used as an emitter material. Examples of suitable emitter materials include, but are not limited to, compounds that can produce emission via phosphorescence, fluorescence, thermally activated delayed fluorescence (i.e., TADF, also known as E-type delayed fluorescence), triplet-triplet annihilation, or a combination of these processes.

[0372] Non-limiting examples of emitter materials that can be used in OLEDs in combination with the materials disclosed herein are illustrated below, along with references disclosing those materials: CN103694277, CN1696137, EB01238981, EP01239526, EP01961743, EP1239526, EP1244155, EP1642951, EP1647554, EP1841834, EP1841834B, EP2062907, EP2730583, JP2012074444, JP201310263, JP4478555, KR1020090133652, KR20120090133653. 032054, KR20130043460, TW201332980, US06699599, US06916554, US20010 019782, US20020034656, US20030068526, US20030072964, US20030138657, US20050123788, US20050244673, US2005123791, US2005260449, US20060008670, US20060065890, US20060127696, US20060134459, US20060134462, U S20060202194, US20060251923, US20070034863, US20070087321, US20070 103060, US20070111026, US20070190359, US20070231600, US2007034863, U S2007104979, US2007104980, US2007138437, US2007224450, US2007278936, US20080020237, US20080233410, US20080261076, US20080297033, US200 805851, US2008161567, US2008210930, US20090039776, US20090108737, U S20090115322, US20090179555, US2009085476, US2009104472, US20100090 591, US20100148663, US20100244004, US20100295032, US2010102716, US20 10105902, US2010244004, US2010270916, US20110057559, US20110108822,US20110204333、US2011215710、US2011227049、US2011285275、US2012292601、US20130146848、US2013033172、US2013165653、US2013181190、US2013334521、US20140246656、US2014103305、US6303238、US6413656、US6653654、US6670645、US6687266、US6835469、US6921915、US7279704、US7332232、US7378162、US7534505、US7675228、US7728137、US7740957、US7759489、US7951947、US8067099、US8592586、US8871361、WO06081973、WO06121811、WO07018067、WO07108362、WO07115970、WO07115981、WO08035571、WO2002015645、WO2003040257、WO2005019373、WO2006056418、WO2008054584、WO2008078800、WO2008096609、WO2008101842、WO2009000673、WO2009050281、WO2009100991、WO2010028151、WO2010054731、WO2010086089、WO2010118029、WO2011044988、WO2011051404、WO2011107491、WO2012020327、WO2012163471、WO2013094620、WO2013107487、WO2013174471、WO2014007565、WO2014008982、WO2014023377、WO2014024131、WO2014031977、WO2014038456、WO2014112450。、

[0373]

[0374]

[0375]

[0376]

[0377]

[0378] f)HBL:

[0379] 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 produce 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 a higher triplet energy than the emitter closest to the HBL interface. In some embodiments, the HBL material has a lower HOMO (further from the vacuum level) and / or a higher triplet energy than one or more hosts closest to the HBL interface.

[0380] In one aspect, the compound used in HBL contains the same molecule or the same functional group used as the host described above.

[0381] In another aspect, the compound used in HBL contains at least one of the following groups in the molecule:

[0382]

[0383] wherein k is an integer from 1 to 20; L 101 is another ligand, and k' is an integer from 1 to 3.

[0384] g)ETL:

[0385] The electron transport layer (ETL) may include a material capable of transporting electrons. The electron transport layer may be intrinsic (undoped) or doped. Doping may be used to enhance conductivity. Examples of ETL materials are not particularly limited, and any metal complex or organic compound may be used as long as it is typically used to transport electrons.

[0386] In one aspect, the compound used in the ETL contains at least one of the following groups in the molecule:

[0387]

[0388] Where R 101 is selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino and combinations thereof; when it is aryl or heteroaryl, it has a similar definition to Ar above. Ar 1 To Ar 3has the same definition as Ar above. k is an integer from 1 to 20. 101 To X 108 is selected from C (including CH) or N.

[0389] In another aspect, the metal complex used in the ETL contains (but is not limited to) the following general formula:

[0390]

[0391] 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.

[0392] Non-limiting examples of ETL materials that can be used in OLEDs in combination with the materials disclosed herein are illustrated below, along with references disclosing those materials: CN103508940, EP01602648, EP01734038, EP01956007, JP2004-022334, JP2005149918, JP2005-268199, KR0117693, KR20130108183, US20040036077, US20070104977, US2007018155, US20090101870, US20090115316, US20090140637, US20090179554, US2009218940, and US2008199. 010108990, US2011156017, US2011210320, US2012193612, US2012214993, US20140 14925, US2014014927, US20140284580, US6656612, US8415031, WO2003060956, WO20 07111263, WO2009148269, WO2010067894, WO2010072300, WO2011074770, WO201110 5373, WO2013079217, WO2013145667, WO2013180376, WO2014104499, WO2014104535,

[0393]

[0394]

[0395]

[0396] h) Charge Generation Layer (CGL)

[0397] 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.

[0398] In any of the above compounds used in each layer of the OLED device, the hydrogen atoms may be partially or fully deuterated. The minimum amount of deuterated hydrogen in the compound is selected from the group consisting of: 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 99% and 100%. Thus, any specific substituent listed, such as but not limited to methyl, phenyl, pyridyl, etc., may be in its non-deuterated, partially deuterated and fully deuterated form. Similarly, the substituent classes (such as but not limited to alkyl, aryl, cycloalkyl, heteroaryl, etc.) may also be in its non-deuterated, partially deuterated and fully deuterated form.

[0399] 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.

[0400] Experimental Examples

[0401] Thermally activated delayed fluorescence (TADF) has received significant attention in recent years as an attractive alternative material family to the current state-of-the-art phosphorescent emitters used in organic light-emitting diodes (OLEDs) (Di, D. et al., Science 2017, 356(6334), 159-163; Romanov, AS et al., Chemistry-A European Journal 2017, 23(19), 4625-4637; Hamze, R. et al., Science 2019, 363(6427), 601-606; Shi, S. et al., Journal of the American Chemical Society Society 2019, 141(8), 3576-3588; Hamze, R. et al., Journal of the American Chemical Society 2019, 141(21), 8616-8626; Romanov, AS et al., Advanced Optical Materials 2018, 6(24), 1801347). The mechanism is based on the upward thermal conversion of triplet excitons to the singlet state via intersystem crossing (ISC). The most widely used singlet-triplet energy gap (ΔE ST ) The smaller strategy is to use T 1 and S 1 The electron-rich fragment (donor, D) and the electron-deficient fragment (acceptor, A) associated with the excited state are highly distorted. The decoupling of the donor and acceptor fragments ensures that not only the exchange energy (K) is minimized, but also the S 1 The radiative rate-dependent extinction coefficient is significantly reduced.

[0402] Carbene metal amide (CMA) compounds are a class of TADF materials with carbenes as acceptors and amides as donors, the carbenes and amides being spatially separated by a metal atom. The two segments can therefore be placed in a coplanar manner to maintain some overlap and achieve a small ΔE ST≤100meV (Hamze, R. et al., Journal of the American Chemical Society 2019, 141(21), 8616-8626). Recent CMAs have the shortest TADF lifetime reported to date (about 250ns) (Muniz, CN et al., Journal of the American Chemical Society 2022, 144(39), 17916-17928). However, the lowest excited state of CMA is inter-ligand charge transfer (ICT), which induces a broadening of the emission spectrum and a full width at half maximum (FWHM) exceeding 70nm. According to the high color purity proposed by Broadcast Service Television 2020 (BT 2020), the wide ICT spectrum limits the application of CMA in OLEDs.

[0403] Multiresonant TADF (MR-TADF) compounds are another attractive alternative to TADF molecules, which show extremely narrow emission (FWHM < 30 nm) through site-specific n, p doping of polycyclic aromatic hydrocarbons (Zhang, Y. et al., Angewandte Chemie International Edition 2019, 58(47), 16912-16917; Hatakeyama, T. et al., Advanced Materials 2016, 28(14), 2777-2781; Kondo, Y. et al., Nature Photonics 2019, 13(10), 678-682; Kim, J. et al., Nature Communications 2020, 11(1), 1765). However, TADF lifetimes are in the microsecond range due to the weak spin-orbit coupling of pure organic molecules.

[0404] Example 1: MR-TADF compounds in the CMA model

[0405] The present disclosure describes a novel class of TADF molecules designed as follows: MR-TADF is built into the CMA model to narrow the FWHM of the emission band, achieve a smaller singlet-triplet splitting, and maintain a larger oscillation intensity. In the novel TADF molecules, the MR-TADF molecules known and unexplored in the literature act as donors and the carbenes known in the literature act as recipients. 10 Metal-separated receptors.

[0406] like Figure 3As shown in , the MR-TADF molecule is based on site-specific n-type doping (e.g. nitrogen or oxygen) and p-type doping (e.g. boron) in a nanographene-like structure. This π-conjugated system can extend from one boron center to two, three boron centers, etc. The examples of MR-TADF donors listed in Type I, Type II, Type III, and Type IV are based on this model. The N-containing portion can be carbazole, benzidine, or N-benzo[d]benzo[4,5]imidazo[1,2-a]-imidazolyl (bim). The O-containing portion is anisole. The N-containing portions in one MR-TADF molecule can be the same or different (e.g. carbazole and benzidine).

[0407] CMA can be constructed using MR-TADFT as a donor. The idea is to exchange the side phenyl groups of benzidine in the MR-TADF molecule (not bonded to the nanographene structure) with carbene-metal groups. Thus, the MR-TADF molecule becomes an amide donor for CMA. Figure 4 A simple example is shown in . Since the exchange of the pendant phenyl groups (red) does not affect the resonance (or special symmetry) of MR-TADF, only the benzidine can bond to the metal. The bonds in the other N- or O-containing moieties contribute to the nanographene structure.

[0408] Based on the number of B atoms in the nanographene structure, MR-TADF molecules are classified into type I, type II, type III and type IV. After each type of MR-TADF molecule, the corresponding CMA is listed: C(I), C(II), C(III), C(IV):

[0409] Generic molecular structure of type I MR-TADF donor (one boron center):

[0410]

[0411] R 1 , R 2 , R 3 = independently represents hydrogen or a substituent selected from the group consisting of deuterium, halogen, pseudohalogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, amide, hydroxy, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, heteroalkynyl, aryl, heteroaryl, nitrile, isonitrile, thiol, borane, acyl, carboxylic acid, benzoyl, ether, ester, vinyl, ketone, sulfinyl, sulfonyl, cyano, phosphino, and combinations thereof; wherein two adjacent R 1 , R 2 and R 3 Can optionally be joined together to form a ring.

[0412] Example of MRTADF Donor I (one boron center):

[0413]

[0414] Examples of corresponding CMA complexes C(I):

[0415] The mononuclear, dinuclear or trinuclear CMAs listed below were designed by exchanging one, two or three side phenyl groups in the type I molecule with carbene-metal moieties. In the dinuclear and trinuclear CMAs, the carbene-metal (CM) moieties can be the same or different (e.g., one CM can be IPr-Au and the other CM can be BZI-Ag) ( Figure 5 ).

[0416] Generic molecular structure of type II MRTADF donors (two boron centers):

[0417]

[0418] R 1 = independently represents hydrogen or a substituent selected from the group consisting of deuterium, halogen, pseudohalogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, amide, hydroxy, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, heteroalkynyl, aryl, heteroaryl, nitrile, isonitrile, thiol, borane, acyl, carboxylic acid, benzoyl, ether, ester, vinyl, ketone, sulfinyl, sulfonyl, cyano, phosphino.

[0419] Examples of MRTADF Donors II:

[0420]

[0421] An example of the corresponding CMA complex C(II) is shown in Figure 6 The basic rule is similar to that of C(I)CMA. The smaller the difference here, the more carbene-metal moieties are available to bond to the MR-TADF donor.

[0422] Generic molecular structure of type III MRTADF donors (three boron centers):

[0423]

[0424] The construction of CMA complex C(III) is similar to that of the CMA listed above. The pattern can be continued for four, five boron centers, etc., and the corresponding CMA complexes are generated.

[0425] Generic molecular structure of type IV MR-TADF donors:

[0426]

[0427] In the literature, the N-type doping sites in the MR-TADF molecule are carbazole, benzidine or anisole. The bim moiety can also be built into MR-TADF as an N-type doping site, which has not yet been patented. The construction strategy is the same as for other N-containing moieties. For one boron center, there are two N sites: two are bim groups; or one is a bim group. Then, you can go to two boron centers and replace the N site with a bim group. An example of a boron center is described here. Example of MRTADF Donor IV

[0428]

[0429] Examples of corresponding CMA complexes:

[0430] Benzidine-based bim MR-TADF molecules can be used as donors for CMA ( Figure 7 ). The pendant phenyl group of benzidine is exchanged with the carbene metal moiety.

[0431] In addition to benzidine, bis-bim can also be used as a donor for CMA to exchange the methyl group with the carbene-metal moiety.

[0432] Example 1

[0433] All calculations were performed using the Q-Chem 5.1 program. Since the excited states involve significant orbital relaxation (or double excitation) after excitation, time-dependent density functional theory (TDDFT) overestimates the S of MR-TADF molecules. 1 . Therefore, the orbitals associated with the optimal excited state are very different from those optimized for the ground state. The restricted open-shell KohnSham method (ROKS) (Kowalczyk, T. et al., The Journal of Chemical Physics 2013, 138(16), 164101) is a method for directly optimizing orbitals to obtain excited states. ROKS calculations were performed on the optimized S1 using the B3LYP / 6-311G** level.

[0434] The excited states of the CMA complex were modeled using density functional theory (DFT) and TDDFT. Geometry optimization was performed using the B3LYP functional and the LACVP* basis set. TDDFT calculations were performed on the geometry-optimized structures using CAM-B3LYP exchange. Natural transition orbitals (NTOs) were generated by singular value decomposition of the transition density matrix using the Q-Chem v5.0 software package.

[0435] Figures 8 to 10 Depicts the biosynthesis of a BIM-based MRTADF molecule (MR-TADF 4-1, Figure 8) and the results of NTO calculations of several CMAs (purple represents holes and yellow represents electrons). Figure 8 Depicted are the NTO results of BIM-based MR-TADF 4-1. Fig. 9 Depicted are the NTO results of the single-core CMA based on MR-TADF 1-1. Fig.10 Depicts the NTO results of the MR TADF 1-1 based binuclear CMA.

[0436] Example 2

[0437] Synthesis adapted from the literature (Chen, Y. et al., Angewandte Chemie International Edition 2020, 59(18), 7122-7130; Agou, T. et al., Organic Letters 2009, 11(16), 3534-3537):

[0438]

[0439] Compound a [bis(2-bromophenyl)amine]: 2-bromoaniline (3.5 g, 20 mmol), 2-bromoiodobenzene (6.33 g, 22 mmol), NaOtBu (5.87 g, 24 mmol), Pd(OAc) 2 (182 mg, 0.08 mmol) and (tBu) 3 A stirred mixture of P (493 mg, 2.4 mmol) in toluene (100 mL) was heated to 120° C. overnight. The solvent was removed in vacuo. The organic phase was extracted with dichloromethane. The crude product was purified by flash column chromatography (pure hexanes) to give compound a (3.99 g, 60%) as a colorless oil. 1 H NMR (400MHz, DMSO-d6) δ (ppm) 7.63 (dd, J=8.0, 1.5Hz, 2H), 7.29 (ddd, J=8.5, 7.5, 1.5Hz, 2H), 7.05 (dd, J=8.1, 1.6Hz, 2H), 7.01 (s, 1H), 6.93 (td, J=7.6, 1.5Hz, 2H).

[0440] Compound b [bis(2,4-dibromophenyl)(methoxymethyl)amine]: 2,2',4,4'-tetrabromodiphenylamine (3.1 g, 9.5 mmol), KOH (2.93 g, 52 mmol), (n-Bu) 4A mixture of NI (0.39 g, 1.0 mmol) and THF (40 mL) was refluxed for 4 h. MOMCl (1.14 g, 14 mmol) was added to the mixture, and the mixture was stirred at room temperature for 24 h. 4 The reaction was quenched with aqueous Cl solution, and THF was removed under reduced pressure. The aqueous layer was extracted with chloroform. The combined organic layers were washed with MgSO 4 Dry and filter.Evaporation of the organic solvent gave compound b (3.5 g, 98%) as a colorless solid. 1 H NMR (400MHz, CDCl3) δ3.25 (s, 3H), 4.91 (s, 2H), 7.05 (dd, J = 8.1, 1.6Hz, 2H), 7.16 (d, J = 8.8Hz, 2H), 7.35 (dd, J = 8.8Hz, 2.0Hz, 2H), 7.69 (d, J = 2.0Hz, 2H).

[0441] Compound c [N-methoxymethylazaborane]: Compound b (0.465 g, 1.25 mmol) was dissolved in THF (20 mL). n-BuLi (2.5 M in hexane, 1 mL, 2.5 mmol) was added at -78°C, and the mixture was stirred for 1 hour. MesB(OMe) 2 (0.265 g, 1.4 mmol) was added to the mixture and the temperature was gradually raised to room temperature. Water was added to the mixture, and the aqueous layer was extracted with chloroform. The combined organic layers were purified by MgSO 4 The organic solvent was removed under reduced pressure and the product was purified by column chromatography (SiO 2 , chloroform / hexane=1:3) to separate the crude material to give compound c (0.125 g, 35%) as a yellow solid. 1 H NMR (400 MHz, CDCl 3 )δ1.95(s,6H),2.40(s,3H),3.67(s,3H),5.77(s,2H),6.94(s,2H),7.13-7.17(m,2H),7.72-7.76(m,4H),7.80(d,J=7.6Hz,2H).

[0442] Compound d [N-hydrogen azacyclohexaborane]: Compound c (0.12 g, 0.35 mmol) was dissolved in THF (10 mL), and aqueous HCl (12 M, 0.3 mL) was added to the solution. The mixture was stirred at room temperature for 2 hours, and Na 2 CO 3 The reaction was quenched with aqueous solution. The aqueous layer was extracted with dichloromethane. The combined organic layers were purified by MgSO 4Dry and filter.Evaporate the organic solvent to give compound d (0.1 g, 100%) as a yellow solid. 1 H NMR (400 MHz, CDCl 3 )δ1.97(s,6H),2.40(s,3H),6.94(s,2H),7.10(t,J=7.6Hz,2H),7.39(d,J=7.6Hz,2H),7.66(t,J=7.6Hz,2H),7.81(d,J=7.6Hz,2H),8.40(s,1H).

[0443] Compound MACAuAzaB: Compound d (0.05 g, 0.17 mmol) and NaOtBu (2 M, 85 mml) were dissolved in THF (20 ml) and stirred at room temperature for 3 hours. MACAuCl (0.011 g, 0.17 mmol) was added to the reaction mixture and stirred for 16 hours. The resulting mixture was filtered through diatomaceous earth, and the solvent was removed under reduced pressure to give a solid. The solid was redissolved in dichloromethane, and hexane was added to precipitate the desired product (0.126 mg, 80%). 1 H NMR (acetone-d6, 400MHz,): 1.24 (d, J=6.8Hz, 6H), 1.36-1.45 (m, 18H), 1.71 (d, J=6.8Hz, 6H), 1.70 (s, 6H),1.78(s,6H),3.29(s,3H),3.29(sept,J=6.8Hz,2H),3.56(sept,J=6.8Hz,2H),4.33(s,2H),6 .64(d,J=8.5Hz,2H),6.73-6.67(m,2H),6.80(s,2H),7.07(ddd,J=8.5,6.8,1.8Hz,2H),7.45(dd ,J=7.8Hz,2H),7.54(d,J=7.8Hz,2H),7.61(d,J=7.8Hz,2H),7.73-7.82(dt,,J=12.9,7.8Hz,2H).

[0444] Photophysics:

[0445] UV-visible spectra were recorded on a HewlettPackard 4853 diode array spectrometer. Steady-state emission measurements were performed using a QuantaMaster Photon Technology International spectrofluorometer. All spectra reported were corrected for the photomultiplier response. Phosphorescence lifetime measurements were performed using time-correlated single photon counting using an IBH Fluorocube instrument equipped with a 405 nm laser excitation source. Quantum yields at room temperature were measured using a Hamamatsu C9920 system equipped with a xenon lamp, a calibrated integrating sphere, and a Model C10027 Photon Multichannel Analyzer (PMA). Spectra are presented in Fig.11 The photophysical values ​​are presented in Table 1.

[0446] All samples in the fluid solution are passed through N 2 Fully bubbling and degassing. Prepare doped polystyrene film by first preparing polystyrene solution. Polystyrene pellets (100 mg) are mixed with 2 mL of toluene and stirred for 1 hour until all PS pellets are dissolved. 1 mg of compound MACAuAzaB is dissolved in this solution. 0.5 mL of the resulting solution is drop-casted on a glass substrate (2 cm × 2 cm) using a pipette to obtain a flat surface. The film is air-dried for 30 minutes and then placed under vacuum for another 12 hours. The thickness of the resulting film is about 200 microns.

[0447] Table 1. Photophysical measurements of MACAuAzaB

[0448]

[0449] Example 2: Achieving fast, narrow and deep blue emission of carbene metalloaryl (aryl = multiresonant molecule) mixed state networks Compound

[0450] The present disclosure seeks to embed inter-ligand charge transfer (ICT) and ligand center (LC) states to produce fast-lived narrow-linewidth emitters, such as Fig.12 Shown on the far right.

[0451] A molecule called BN was used as a proof-of-concept for this idea. Fig.13 Shown are the computational screening of BN and the chemical structures of the two carbene metallaryls (aryl = multiresonant molecules) investigated in this study.

[0452] This computational study shows that BZAC will be LC-dominated in nature, while PZI will produce state hybridization when combined with BN. This will cause interactions between the ICT state and the LC state, which will greatly shorten the lifetime. However, if the emission comes from the ICT state, there will also be a broadening of the linewidth. A compromise between narrow linewidth and fast emission can be achieved through carbene selection, structural modification, and solvent selection. The data for BZAC-Au-BN are shown in Fig.14 and Table 2.

[0453] Table 2. Photophysical data of BZAC-Au-BN in different solvents.

[0454]

[0455] BZAC-Au-BN shows metal perturbation multiresonant behavior with narrow linewidth, high PLQY and slightly faster lifetime than BN alone. Solvent polarity shows minimal effect on the photophysical data, indicating that the emission is from the LC state. In the polymer matrix, the lifetime changes from biexponential to single exponential. For comparison, the photophysical data for PZI-Au-BN are shown in Fig.15 The photophysical data are presented in Table 3.

[0456] Table 3. Photophysical data of PZI-Au-BN in different solvents

[0457]

[0458] [a] Measured by comparison with BN

[0459] Except the shoulder peak near 400nm, PZI-Au-BN shows a very similar absorption spectrum compared with BZAC-Au-BN. This shoulder peak may come from the ICT state close in PZI-Au-BN, which is not present in BZAC-Au-BN. Depending on the solvent, this ICT state close strongly interferes with the emission curve of PZI-Au-BN. In MeCyHx, there is a wide feature showing as a shoulder peak at 510nm. It moves to 530nm in toluene and moves to 545nm in MeTHF. Wide emission and strong solvation color development indicate the emission from the ICT state. The lifespan in MeCyHx, toluene and MeTHF is multi-exponential, and the contribution of a considerable part comes from the sub-microsecond lifespan. The sub-microsecond, single-exponential lifespan shown in Table 4 is obtained by measuring the lifespan at the right edge of the emission curve.

[0460] Table 4. Sub-microsecond lifetimes measured from the right side of the emission curves in different solvents.

[0461] Complex Solvents <![CDATA[λ Em (nm)]]> <![CDATA[τ 298K ]]> PZI-Au-BN HkDJ 530 420ns PZI-Au-BN Toluene 560 870ns PZI-Au-BN MeTHF 585 620ns

[0462] These lifetimes are an order of magnitude faster than those of BZAC-Au-BN, indicating that the ICT state emits much faster. The trade-off for emission from the ICT state is that the emission linewidth is much wider. However, in MeCyHx, the LC state and the ICT state appear to be close, resulting in a fast lifetime and a slightly narrow emission linewidth. Nesting the LC state and the ICT state closer should produce sub-microsecond lifetimes and narrow emission linewidths. In addition, if the PZI-Au-BN is placed in a polymer matrix, the lifetime may be shortened to the faster component, as seen in BZAC-Au-BN, and the FWHM is reduced. This data provides proof of concept for the carbenes metal aryl mixed state patent by achieving sub-microsecond lifetimes and providing a deep understanding of the simultaneous realization of narrow emission linewidths by nesting LC and ICT states.

Claims

1. A metal complex of formula I, in Y is N or B; X a1 , X a2 and X a3 Each is N or CR a ; X b1 , X b2 and X b3 Each is N or CR b ; X c1 , X c2 and X c3 Each is N or CR c ; Z a , Z b and Z c Independently selected from the group consisting of: single bond, NR N , O, C(O), BR B , S or no key; condition is Z a , Z b and Z c No more than two of them indicate no key; R a , R b and R c Each represents a single substitution to the maximum number of substitutions allowed, or no substitution; One, two or three occurrences of R N , R B , R a , R b and R c represents a bond to a metal M selected from the group consisting of Ir, Pt, Pd, Ru, Cu, Ag and Au; M is further coordinated with one or more neutral ligands L or anionic ligands L' to satisfy the valence of M, provided that the metal complex of formula I is neutral; R does not represent a bond to the metal M N , R B , R a , R b and R c is independently at each occurrence hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, nitrile, isonitrile, thiol, borane, acyl, carboxylic acid, ether, ester, sulfinyl, sulfonyl, cyano, phosphino, and combinations thereof; and wherein any two adjacent substituents are optionally joined or fused together to form an optionally substituted ring.

2. The metal complex according to claim 1, wherein the complex has a structure of formula II: in Z b ' is N or B; Q 1 and Q 2 each independently represents CR, CRR', O, NR, N, S, Se, Br, BRR', SiRR', 1,2-arylene or 1,2-heteroarylene; The condition is that when Q 2 When Q represents 1,2-phenylene, 1 does not represent CRR'; and when Q 1 When Q represents 1,2-phenylene, 2 It does not indicate CRR'; Each R and R' is independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, nitrile, isonitrile, thiol, borane, acyl, carboxylic acid, ether, ester, sulfinyl, sulfonyl, cyano, phosphino, and combinations thereof.

3. The metal complex according to claim 1, wherein Z a , Z b and Z c At least one of them independently represents Y' and together with the adjacent phenylene ring forms a group of formula A: in Y' is N or B; R A indicates a single substitution up to the maximum number of substitutions allowed, or no substitution; and Each R A are independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, nitrile, isonitrile, thiol, borane, acyl, carboxylic acid, ether, ester, sulfinyl, sulfonyl, cyano, phosphino, and combinations thereof. The metal complex according to claim 1 , wherein Y is B.

5. The metal complex according to claim 1, wherein the metal complex is represented by formula III: in: Z d , Z e and Z f Independently selected from the group consisting of: single bond, NR N , O, C(O), BR B , S and keyless; X d1 , X d2 and X d3 Each independently is N or CR d ; X e1 , X e2 and X e3 Each independently is N or CR e ; One, two or three occurrences of R N , R B , R a , R b , R c , R d and R e represents a bond to the metal M; Each R not representing a bond to the metal M N , R B , R a , R b , R c , R d and R e are independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, nitrile, isonitrile, thiol, borane, acyl, carboxylic acid, ether, ester, sulfinyl, sulfonyl, cyano, phosphino, and combinations thereof; and wherein any two adjacent substituents are optionally joined or fused together to form an optionally substituted ring.

6. The metal complex according to claim 1, wherein the metal complex is represented by formula IIIa: X d1 , X d2 and X d3 Each is N or CR d ; X e1 , X e2 and X e3 Each is N or CR e ; One, two or three occurrences of R a , R c , R d and R e represents a bond to the metal M; Each R not representing a bond to the metal M d and R e are independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, nitrile, isonitrile, thiol, borane, acyl, carboxylic acid, ether, ester, sulfinyl, sulfonyl, cyano, phosphino, and combinations thereof; wherein any two adjacent substituents are optionally joined or fused together to form an optionally substituted ring.

7. The metal complex according to claim 1, wherein the metal complex is represented by Formula IV: in: Z a ' and Z b ' is independently present or absent, and if present, independently represents B or N; Z d , Z e , Z f and Z g Independently selected from the group consisting of: single bond, NR N , O, C(O), BR B , S and keyless; X d1 , X d2 and X d3 Each independently is N or CR d ; X e1 , X e2 and X e3 Each independently is N or CR e ; One, two or three occurrences of R N , R B , R a , R b , R c , R d and R e represents a bond to the metal M; Each R not representing a bond to the metal M N , R B , R a , R b , R c , R d and R e are independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, nitrile, isonitrile, thiol, borane, acyl, carboxylic acid, ether, ester, sulfinyl, sulfonyl, cyano, phosphino, and combinations thereof; and wherein any two adjacent substituents are optionally joined or fused together to form an optionally substituted ring.

8. The metal complex according to claim 1, wherein the metal complex is represented by Formula V: Z a ' and Z b ' is independently present or absent, and if present, independently represents B or N; Y' and Y" are independently B or N; Z d , Z e , Z f and Z g Independently selected from the group consisting of: single bond, NR N , O, C(O), BR B , S and keyless; X d1 , X d2 and X d3 Each independently is N or CR d ; X e1 , X e2 and X e3 Each independently is N or CR e ; X f1 , X f2 and X f3 Each independently is N or CR f ; X g1 , X g2 and X g3 Each independently is N or CR g ; One, two or three occurrences of R N , R B , R a , R b , R c , R d , R e , R f or R g represents a bond to the metal M; Each R not representing a bond to the metal M N , R B , 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 deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, nitrile, isonitrile, thiol, borane, acyl, carboxylic acid, ether, ester, sulfinyl, sulfonyl, cyano, phosphino, and combinations thereof; and wherein any two adjacent substituents are optionally joined or fused together to form an optionally substituted ring.

9. The metal complex according to claim 1, wherein the metal complex is represented by Formula VI: Z c 'Exists or does not exist, and if present, it means B or N; Y' is B or N; Z d and Z e Independently selected from the group consisting of: single bond, NR N , O, C(O), BR B , S and keyless; X d1 , X d2 and X d3 Each independently is N or CR d ; X e1 , X e2 and X e3 Each independently is N or CR e ; One, two or three occurrences of R N , R B , R a , R b , R c , R d or R e represents a bond to the metal M; Each R not representing a bond to the metal M N , R B , R a , R b , R c , R d and R e are independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, nitrile, isonitrile, thiol, borane, acyl, carboxylic acid, ether, ester, sulfinyl, sulfonyl, cyano, phosphino, and combinations thereof; and wherein any two adjacent substituents are optionally joined or fused together to form an optionally substituted ring.

10. The metal complex according to claim 1, wherein the metal complex is represented by one of the following structures: One, two or three occurrences of R N , R a , R b , R c , R d , R e or R f independently represent a bond to the metal M; wherein R which does not represent a bond to the metal M N , R a , R b , R c , R d , R e and R f is independently at each occurrence hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, nitrile, isonitrile, thiol, borane, acyl, carboxylic acid, ether, ester, sulfinyl, sulfonyl, cyano, phosphino, and combinations thereof. The metal complex according to claim 1 , wherein the metal M is monovalent and each metal M is independently bound to a neutral carbene ligand L. 14 .

12. The metal complex according to claim 11, wherein each neutral carbene ligand L is independently selected from the group consisting of: Formula B, Formula C, Formula D, Formula E, Formula F and Formula G: in X 1 To X 4 Each independently represents NR 1 , CR 1 R 2 , C=O, C=S, O or S; and R 1 and R 2 is independently selected at each occurrence from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, nitrile, isonitrile, thiol, borane, acyl, carboxylic acid, ether, ester, sulfinyl, sulfonyl, cyano, phosphino, and combinations thereof; Any two adjacent R 1 and R 2 are optionally joined or fused together to form an optionally substituted ring; Each X 1 and X 4 Independently represent N, NR 1 , CR 1 , CR 1 R 2 、SiR 1 、SiR 1 R 2 , PR 1 , B, BR 1 , BR 1 R 2 , O or S; and Each X 2 and X 3 Independently express CR 1 , CR 1 R 2 、SiR 1 、SiR 1 R 2 , N, NR 1 ,P,PR 1 , B, BR 1 , O or S; R 1 and R 2 is independently at each occurrence hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, nitrile, isonitrile, thiol, borane, acyl, carboxylic acid, ether, ester, sulfinyl, sulfonyl, cyano, phosphino, and combinations thereof; Any two adjacent R 1 and R 2 are optionally joined or fused together to form an optionally substituted ring; and Dashed lines within a five-membered ring represent zero or one double bond; Where X 1 and X 2 Each independently represents NR 1 , CR 1 R 2 , O or S; R 1 and R 2 is independently at each occurrence hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, nitrile, isonitrile, thiol, borane, acyl, carboxylic acid, ether, ester, sulfinyl, sulfonyl, cyano, phosphino, and combinations thereof; and Any two adjacent R 1 and R 2 are optionally joined or fused together to form an optionally substituted ring; in Each X 1 To X 5 Independently represent N, P, NR 1 , PR 1 , B, BR 1 , CR 1 、SiR 1 , CR 1 R 2 、SiR 1 R 2 , C=O, C=S, O or S; n is 0 or 1; R 1 and R 2 is independently at each occurrence hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, nitrile, isonitrile, thiol, borane, acyl, carboxylic acid, ether, ester, sulfinyl, sulfonyl, cyano, phosphino, and combinations thereof; Any two adjacent R 1 and R 2 are optionally joined or fused together to form an optionally substituted ring; in Each X 1 and X 4 Independently represents NR 1 , CR 1 、SiR 1 , CR 1 R 2 、SiR 1 R 2 , PR 1 , BR 1 , C=O, C=S, O or S; Each X 2 and X 3 independently present or absent, and if present, independently represents H, NR 1 R 2 , CR 1 , CR 1 R 2 , C=O, C=S, O or S; R 1 and R 2 is independently at each occurrence hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, nitrile, isonitrile, thiol, borane, acyl, carboxylic acid, ether, ester, sulfinyl, sulfonyl, cyano, phosphino, and combinations thereof; Any two adjacent R 1 and R 2 are optionally joined or fused together to form an optionally substituted ring Where X 1 To X 8 Represents N, P, NR independently at each occurrence 1 , PR 1 , B, BR 1 , CR 1 、SiR 1 , CR 1 R 2 、SiR 1 R 2 、C═O, C═S, O or S; n is 1 or 2; R 1 and R 2 is independently at each occurrence hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, nitrile, isonitrile, thiol, borane, acyl, carboxylic acid, ether, ester, sulfinyl, sulfonyl, cyano, phosphino, and combinations thereof; Any two adjacent R 1 and R 2 are optionally joined or fused together to form an optionally substituted ring.

13. The metal complex according to claim 11, wherein each neutral carbene ligand L is independently represented by one of the following structures: wherein each R is independently selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, amide, hydroxy, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, heteroalkynyl, aryl, heteroaryl, nitro, nitrile, isonitrile, thiol, borane, acyl, carboxylic acid, benzoyl, ether, ester, vinyl, ketone, sulfinyl, sulfonyl, cyano, phosphino, and combinations thereof; wherein two adjacent substituents may be joined together to form a ring.

14. The metal complex according to claim 11, wherein each neutral carbene ligand L is independently represented by one of the following structures: Among them, each R 1 , R 2 and R 3 independently selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, amide, hydroxy, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, heteroalkynyl, aryl, heteroaryl, nitro, nitrile, isonitrile, thiol, borane, acyl, carboxylic acid, benzoyl, ether, ester, vinyl, ketone, sulfinyl, sulfonyl, cyano, phosphino, and combinations thereof; wherein two adjacent substituents may be joined together to form a heteroaryl ring, an aromatic ring, a cycloalkyl ring, or a bicyclic ring; and wherein each Ar independently represents an aryl or heteroaryl group, which is optionally further substituted with one or more substituents independently selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, amide, hydroxy, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, heteroalkynyl, aryl, heteroaryl, nitro, nitrile, isonitrile, thiol, borane, acyl, carboxylic acid, benzoyl, ether, ester, vinyl, ketone, sulfinyl, sulfonyl, cyano, phosphino, and combinations thereof; wherein any two adjacent substituents may be joined together to form a ring.

15. The metal complex according to claim 11, wherein each neutral carbene ligand L is independently represented by one of the following structures: Where dipp = 2,6-diisopropylphenyl.

16. An organic light emitting device (OLED), comprising: anode; cathode; and An organic layer disposed between the anode and the cathode, the organic layer comprising a metal complex of Formula I: in Y is N or B; X a1 , X a2 and X a3 Each is N or CR a ; X b1 , X b2 and X b3 Each is N or CR b ; X c1 , X c2 and X c3 Each is N or CR c ; Z a , Z b and Z c Independently selected from the group consisting of: single bond, NR N , O, C(O), BR B , S or no key; condition is Z a , Z b and Z c No more than two of them indicate no key; R a , R b and R c Each represents a single substitution to the maximum number of substitutions allowed, or no substitution; One, two or three occurrences of R N , R B , R a , R b and R c represents a bond to a metal M selected from the group consisting of Ir, Pt, Pd, Ru, Cu, Ag and Au; M is further coordinated with one or more neutral ligands L or anionic ligands L' to satisfy the valence of M, provided that the metal complex of formula I is neutral; R does not represent a bond to the metal M N , R B , R a , R b and R c is independently at each occurrence hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, nitrile, isonitrile, thiol, borane, acyl, carboxylic acid, ether, ester, sulfinyl, sulfonyl, cyano, phosphino, and combinations thereof; and wherein any two adjacent substituents are optionally joined or fused together to form an optionally substituted ring.

17. The OLED according to claim 16, wherein the organic layer further comprises a host, wherein the host comprises at least one chemical group selected from the group consisting of: triphenylene, carbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, azatriphenylene, azacarbazole, aza-dibenzothiophene, aza-dibenzofuran and aza-dibenzoselenophene.

18. A consumer product comprising the OLED according to claim 16; The consumer product is a flat panel display, a curved display, a computer monitor, a medical monitor, a television, a billboard, interior or exterior lighting and / or signaling, a head-up display, a fully or partially transparent display, a flexible display, a rollable display, a foldable display, a stretchable display, a laser printer, a phone, a mobile phone, a tablet computer, a tablet phone, a personal digital assistant (PDA), a wearable device, a laptop computer, a digital camera, a camcorder, a viewfinder, a microdisplay (a display with a diagonal of less than 2 inches), a 3-D display, a virtual reality or augmented reality display, a vehicle, a video wall comprising multiple displays tiled together, a theater or stadium screen, a light therapy device or a sign.

19. A metal complex represented by formula VII: Ring A is a multi-ring structure capable of producing thermally activated delayed fluorescence; each M is independently a metal selected from the group consisting of Au, Ag and Cu; Each [carbene] independently represents a carbene ligand; n is an integer having a value from 1 to 6; wherein the compound is neutral; Ring A has a singlet excitation energy S1 centered on the first ligand LC and the triplet excitation energy T1 centered on the first ligand LC ; Where M has the first charge transfer excited state S1 CT and the first charge transfer triplet excited state T1 CT ;and Among them, T1 CT and S1 LC The energy difference between them is ≤200meV.

20. The metal complex according to claim 19, wherein T1 CT and S1 LC The energy difference between them is ≤100meV.

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