D10 metal carbene complexes for oled applications

Abstract

Described herein are two-coordinate d10 metal carbene complexes comprising (i) Cu(I), Ag(I), or Au(I), (ii) a pyrazine-fused NHC ligand or a pyridine-fused NHC ligand, and (iii) a carbazole ligand, a pyrido[2,3-b]indole ligand, or a pyrido[3,4-b]indole ligand. The radiative properties of the compounds can be controlled through thermally activated delayed fluorescence. The emission color of the complexes can be tuned through the use of carbazoles with different donor strengths. Methods of using the complexes are also described herein.

Description

[0001] Cross-reference to related applications

[0002] This application claims the benefit and priority of U.S. Provisional Application No. 63 / 282,496, filed November 23, 2021, the entire contents of which are incorporated herein by reference. Technical Field

[0003] This invention generally relates to the field of luminescent d10 metal carbene complexes, particularly d10 metal carbene complexes containing (i) pyrazine-fused N-heterocyclic carbene ligands or pyridine-fused N-heterocyclic carbene ligands and (ii) carbazole ligands or α-, β-, γ- or δ-carboline ligands, and the use of these complexes in organic light-emitting devices (OLEDs). Background Technology

[0004] Transition metal complexes have garnered significant attention in both commercial and academic fields as molecular probes, catalysts, and luminescent materials. As luminescent materials, transition metal complexes are increasingly being explored as potential alternatives to purely organic materials due to their potential for improved luminescence efficiency and device stability.

[0005] Currently, ring-metallized iridium(III) and platinum(II) phosphors are among the most competitive candidates for commercial OLED emitters. However, the development of metal-based or organic thermally activated delayed fluorescence (TADF) emitters lags behind, primarily due to their lower stability, which affects device lifetime. For practical applications, it is essential to improve the device performance and operational stability / lifetime of metal-based OLEDs. Several studies have described d10 complexes for use as OLED emitters. These include US Patent 9,773,986 by Thompson et al.; European Patent Application Publication 3,489,243 by Thompson et al.; US Patent Application Publication 2015 / 0108451 and 2019 / 0161504 by Thompson et al.; and CN112794863. However, these studies have not reported results regarding device lifetime. Other studies include complexes of Cu(I), Ag(I), or Au(I), involving carbene ligands and carbazoles, for example: Hamze et al., Science 2019, 363, 601–606; Shi et al., J. Am. Chem. Soc. 2019, 141, 3576–3588; Hamze et al., J. Am. Chem. Soc. 2019, 141, 21, 8616–8626; Li et al., Angew. Chem. Int. Ed. 2020, 59, 8210–8217; and Hamze et al., Front. Chem. 2020, 8:401. However, some complexes exhibit phosphorescent properties, resulting in lower radiative attenuation rates. For example, the IPr-Cu-Cz and IMes-Cu-Cz complexes (Angew. Chem. Int. Ed. 2020, 59, 8210-8217) exhibit long-lifetime room-temperature phosphorescence with lifetimes in the millisecond range.

[0006] Therefore, there is still a need to develop improved and more efficient transition metal complexes to enable products incorporating OLEDs to achieve higher efficiency.

[0007] Therefore, one object of the present invention is to provide new and improved luminescent transition metal dicoordinate complexes containing d10 metal. Summary of the Invention

[0008] This article describes dicoordinated d10 metal carbene complexes comprising (i) Cu(I), Ag(I), or Au(I), (ii) pyrazine-fused N-heterocyclic carbene (NHC) ligands or pyridine-fused N-heterocyclic carbene ligands, and (iii) carbazole ligands, pyridine[2,3-b]indole ligands, or pyridine[3,4-b]indole ligands. The radiometric properties of these compounds can be controlled by TADF. The emission color of these compounds can also be tuned by using carbazole, pyrido[2,3-b]indole, or pyrido[3,4-b]indole with different donor strengths.

[0009] The compounds of this invention have the following structures:

[0010]

[0011] in:

[0012] D represents carbon.

[0013] T, J, and W are independently carbon or nitrogen, wherein at least one of T, J, and W is nitrogen, wherein J is nitrogen when T is carbon, or J is carbon when T is nitrogen, and T, J, and W are bonded to a hydrogen atom or not bonded to a hydrogen atom depending on their valence.

[0014] Each Ra is independently hydrogen, an unsubstituted alkyl group, or a substituted alkyl group.

[0015] Each Rb is independently an unsubstituted alkyl or a substituted alkyl.

[0016] X and Y are nitrogen.

[0017] L represents no bond or a single bond.

[0018] CY3 and CY4 are independently unsubstituted aryl, substituted aryl, unsubstituted heteroaryl, substituted heteroaryl, and substituted C3-C. 20 Cycloalkenyl, unsubstituted C3-C 20 Cycloalkenyl groups or combinations thereof, and

[0019] R1 and R2 are hydrogen, or R1, J, D and R2 together form an unsubstituted aryl, a substituted aryl, an unsubstituted heteroaryl or a substituted heteroaryl.

[0020] In some forms, the compounds of the present invention have the following structures:

[0021]

[0022] in:

[0023] (i) M=Cu(I); W=N; Ra=H; U=CH; V=V"=carbon; Rv=H; R7=R8=H;

[0024] (ii) M=Cu(I); W=N; Ra=H; U=CH; V=V"=carbon; Rv=H; R7=H; R8=CN;

[0025] (iii) M = Cu(I); W = N; Ra = H; U = CH; V = V" = carbon; Rv = H; R7 = R8 = tert-butyl;

[0026] (iv) M = Cu(I); W = N; Ra = H; U = CH; V = V" = carbon; Rv = H; R7 = R8 = phenyl;

[0027] (v)M=Cu(I); W=N; Ra=H; U=CH; V=N; V"=carbon; Rv=None; R7=R8=H;

[0028] (vi) M = Cu(I); W = U = CH; V = V" = carbon; Rv = H; Ra = isopropyl; R7 = R8 = H;

[0029] (vii) M = Cu(I); W = N; Ra = H; U = CH; V = V" = carbon; R8 = H; Rv and R7 form together.

[0030]

[0031] (viii) M = Cu(I); W = U = CH; Ra = isopropyl; V = V" = carbon; R8 = H; Rv and R7 form together

[0032]

[0033] (ix) M=Cu(I); W=N; Ra=H; U=CH; V=V"=carbon; Rv=H; R7=R8=H;

[0034] (x)M=Cu(I); W=N; Ra=H; U=CH; V=V"=carbon; Rv=H; R7=H; R8=F;

[0035] (xi)M=Cu(I); W=N; Ra=H; U=CH; V=V"=carbon; Rv=H; R7=R8=methyl;

[0036] (xii) M=Au(I); W=N; Ra=H; U=CH; V=carbon; Rv=H; V"=carbon; R7=R8=H;

[0037] (xiii) M = Au(I); W = N; Ra = H; U = CH; V = carbon; Rv = H; V" = carbon; R7 = H; R8 = CN;

[0038] (xiv)M=Au(I);W=N;Ra=H;U=N;V=carbon;Rv=H;V"=carbon;R7=R8=H;

[0039] (xv)M=Au(I);W=U=CH;V=carbon;Rv=H;Ra=isopropyl;V"=carbon;R7=R8=H;

[0040] (xvi)M=Au(I);W=N;Ra=H;U=CH;V=N;Rv=none;V"=carbon;R7=R8=H;

[0041] (xvii) M=Au(I); W=N; Ra=H; U=CH; V=V"=carbon; Rv=H; R7=R8=CN;

[0042] (xviii) M = Au(I); W = N; Ra = hydrogen; U = CH; V = V" = carbon; R8 = H; Rv and R7 form together

[0043]

[0044] (xix)M=Au(I); W=U=CH; Ra=isopropyl; V=V"=carbon; Rv=H; R7=R8=tert-butyl;

[0045] (xx)M=Au(I);W=U=CH;Ra=isopropyl;V=V"=carbon;Rv=H;R7=H;R8=F;

[0046] (xxi)M=Au(I); W=N; U=CH; Ra=H; V=V"=carbon; Rv=H; R7=R8=H;

[0047] (xxii)M=Au(I);W=N;U=CH;Ra=H;V=V"=carbon;Rv=H;R7=R8=tert-butyl;

[0048] (xxiii) M=Ag(I); W=N; U=CH; Ra=H; V=V"=carbon; Rv=H; R7=R8=H;

[0049] For (i), (ii), (iii), (iv), (v), (vi), (vii), (viii), (xii), (xiii), (xiv), (xv), (xvi), (xvii), (xviii), (xix), (xx), and (xxiii), the dashed line indicates that there is no key.

[0050] For (ix), (x), (xi), (xxi), and (xxii), the dashed lines indicate the presence of a bond.

[0051] The compounds of this invention may be included in organic light-emitting devices for commercial applications. Attached Figure Description

[0052] Figure 1 The chemical structures of metal carbene complexes representing Cu1, Cu2, Cu3, Cu4, Cu5, Cu6, Cu7, Cu8, Cu9, Cu10, Cu11, Au1, Au2, Au3, Au4, Au5, Au6, Au7, Au8, Au9, Au10, Au11 and Ag1 are shown.

[0053] Figure 2A , 2B 2C, 2D, 2E and 2F respectively show Figure 1 The crystal structures of Au1, Au4, Au8, Au9, Cu3, and Cu6 are shown.

[0054] Figures 3A-3D This is a line graph showing the electroluminescence spectra and performance characteristics of Cu1-based devices with doping concentrations of 2-8 wt% wt%. Device structure: ITO / HAT-CN (5nm) / TAPC (40nm) / TCTA (10nm) / TCTA:TPBi:Cu1 (20nm) / TPBi (50nm) / LiF (1nm) / Al (100nm).

[0055] Figures 4A-4D This is a line graph showing the electroluminescence spectrum and performance characteristics of devices doped with Cu2 at concentrations of 2-6 wt / wt%. Device structure: ITO / HAT-CN (5nm) / TAPC (40nm) / TCTA (10nm) / TCTA:DPEPO:Cu2 (20nm) / DPEPO (10nm) / TPBi (40nm) / LiF (1nm) / Al (100nm).

[0056] Figures 5A-5D This is a line graph showing the electroluminescence spectrum and performance characteristics of devices doped with Cu3 at concentrations of 2-6 wt / wt%. Device structure: ITO / HAT-CN (5nm) / TAPC (40nm) / TCTA (10nm) / TCTA:TPBi:Cu3 (20nm) / TPBi (50nm) / LiF (1nm) / Al (100nm).

[0057] Figures 6A-6DThis is a line graph showing the electroluminescence spectrum and performance characteristics of devices doped with Au1 at concentrations of 2-6 wt / wt%. Device structure: ITO / HAT-CN (5nm) / TAPC (40nm) / TCTA (10nm) / TCTA:TPBi:Au1 (20nm) / TPBi (50nm) / LiF (1nm) / Al (100nm).

[0058] Figures 7A-7D This is a line graph showing the electroluminescence spectrum and performance characteristics of devices doped with Au2 at concentrations of 2-6 wt / wt%. Device structure (I): ITO / HAT-CN (5nm) / TAPC (40nm) / TCTA (10nm) / TCTA:TPBi:Au2 (20nm) / TPBi (50nm) / LiF (1nm) / Al (100nm).

[0059] Figures 8A-8D This is a line graph showing the electroluminescence spectrum and performance characteristics of devices doped with Au2 at concentrations of 2-8 wt / wt%. Device structure (II): ITO / HAT-CN (5nm) / TAPC (40nm) / TCTA (10nm) / TCTA:DPEPO:Au2 (20nm) / DPEPO (10nm) / TPBi (40nm) / LiF (1nm) / Al (100nm).

[0060] Figure 9 This is a line graph showing the emission spectrum of Cu4.

[0061] Figure 10 This is a line graph showing the emission spectrum of Au3.

[0062] Figure 11 This is a line graph showing the emission spectrum of Cu5.

[0063] Figure 12A and 12B This is a line graph showing the emission spectra of Cu6 and Au4.

[0064] Figures 13A-13C This is a line graph showing the device data for Cu2 in Table 5b. The EL spectrum and performance characteristics of the device with a Cu2 doping concentration of 2 wt / wt%. Device structure: ITO / HAT-CN (5nm) / PT-301 (160nm) / PT-603I (5nm) / Cu2:LLP604 (20nm) / PT74M (5nm) / LET321:Liq (1:1, 25nm) / Liq (1nm) / Al (100nm).

[0065] Figures 14A-14DThis is a line graph showing the EL spectrum and performance characteristics of devices with Cu3 doping concentrations of 2-6 wt / wt%. Device structure (II): ITO / HAT-CN (5nm) / PT-301 (160nm) / EB (5nm) / Cu3:RH (40nm) / HB (5nm) / ZADN:Liq (35:65,35nm) / Liq (1nm) / Al (100nm).

[0066] Figures 15A-15D This is a line graph showing the EL spectrum and performance characteristics of devices with Cu4 doping concentrations of 2-6 wt / wt%. Device structure (I): ITO / HAT-CN (5nm) / TAPC (40nm) / TCTA (10nm) / TCTA:TPBi:Cu4 (20nm) / TPBi (50nm) / LiF (1nm) / Al (100nm).

[0067] Figures 16A-16D This is a line graph showing the EL spectrum and performance characteristics of devices with Cu4 doping concentrations of 2-6 wt / wt%. Device structure (II): ITO / HAT-CN (5nm) / PT-301 (160nm) / PT-603I (5nm) / Cu4:LLP604 (20nm) / PT74M (5nm) / LET321:Liq (1:1, 25nm) / Liq (1nm) / Al (100nm).

[0068] Figures 17A-17D This is a line graph showing the EL spectrum and performance characteristics of devices doped with Au2 at concentrations of 2-8 wt / wt%. Device structure (III): ITO / HAT-CN (5nm) / PT-301 (160nm) / PT-603I (5nm) / Au2:LLP604 (20nm) / PT74M (5nm) / LET321:Liq (1:1, 25nm) / Liq (1nm) / Al (100nm).

[0069] Figure 18 This is a line graph showing the emission spectrum of Cu7 (in an MCP film).

[0070] Figure 19 This is a line graph showing the emission spectrum of Cu8 (in an MCP film).

[0071] Figure 20 This is a line graph showing the emission spectrum of Cu9 (in degassed toluene and MCP film).

[0072] Figure 21 This is a line graph showing the emission spectrum of Au7 (2wt / wt% in PMMA film).

[0073] Figures 22A-22D This is a line graph showing the EL spectra and performance characteristics of devices doped with Cu6 (in a TCTA:DPEPO co-body) at concentrations of 2-6 wt / wt%. Device structure: ITO / HAT-CN (5nm) / TAPC (40nm) / TCTA (10nm) / TCTA:DPEPO:Cu6 (20nm) / DPEPO (10nm) / TPBi (40nm) / LiF (1.2nm) / Al (100nm).

[0074] Figures 23A-23D This is a line graph showing the EL spectrum and performance characteristics of a vapor-deposited superfluorescent OLED with Cu6 and v-DABNA (in mCBP). Device structure: ITO / HAT-CN (10nm) / BPBPA (120nm) / mCBP (10nm) / mCBP:Cu6:v-DABNA (20nm) / SF3-TRz (5nm) / SF3-TRz:Liq (1:1, 25nm) / Liq (2nm) / Al (100nm).

[0075] Figures 24A-24D This is a line graph showing the EL spectrum and performance characteristics of Cu7 (in a DMIC-Cz:DMIC-Trz co-body) with a doping concentration of 2-6 wt / wt%. Device structure: ITO / HAT-CN (10nm) / BPBOA (80nm) / FSF4A (5nm) / DMIC-Cz:DMIC-Trz:Cu7 (30nm) / ANT-Biz (5nm) / ANT-Biz:Liq (25nm) / Liq (2nm) / Al (100nm).

[0076] Figures 25A-25D This is a line graph showing the EL spectrum and performance characteristics of Cu7 and MR-R (in RH) vapor-deposited superfluorescent OLEDs. Device structure: ITO / HAT-CN (10nm) / HT (40nm) / EB (5nm) / Cu7:MR-R:RH (40nm) / HB (5nm) / ZADN:Liq (35:65) (35nm) / Liq (2nm) / Al (100nm).

[0077] Figures 26A-26D This is a line graph showing the EL spectrum and performance characteristics of a vapor-deposited superfluorescent OLED containing Au3 and BN-2 (in mCBP). Device structure: ITO / HAT-CN (5nm) / TAPC (40nm) / mCBP (10nm) / Au3:BN-2:mCBP (20nm) / PPF (10nm) / TmPyPb (40nm) / LiF (1.2nm) / Al (100nm).

[0078] Figures 27A-27D This is a line graph showing the EL spectra and performance characteristics of Au5 (in the mCBP:CzSiTrz co-body) with doping concentrations of 2-8 wt / wt%. Device structure: ITO / HAT-CN (10 nm) / FSFA (120 nm) / mCBP (10 nm) / mCBP:CzSiTrz:Au5 (30 nm) / SF3-Trz (5 nm) / SF3-Trz:Liq (25 nm) / Liq (2 nm) / Al (100 nm).

[0079] Figure 28 This is a line graph showing the emission spectrum of Au10 (in an MCP film).

[0080] Figure 29 This is a line graph showing the emission spectrum of Au11 (in an MCP film). Detailed Implementation

[0081] I. Definition

[0082] "alkyl" includes straight-chain and branched alkyl groups, as well as cycloalkyl groups having a cyclic structure. Preferred alkyl groups are those containing one to eighteen carbon atoms, including methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, and other similar compounds. Furthermore, the alkyl group may optionally be substituted with one or more substituents selected from hydrogen, deuterium, formaldehyde, cyano, alkylynyl, substituted alkylynyl, arylynyl, substituted arylynyl, heteroarylynyl, substituted heteroarylynyl, condensed polycyclic, substituted condensed polycyclic, aryl, alkyl, heteroaryl, nitro, trifluoromethane, cyano, aryl ether, alkyl ether, heteroaryl ether, diarylamine, dialkylamine, dihexarylamine, diarylborane. Alkyl, triarylsilane, trialkylsilane, alkenyl, alkylaryl, cycloalkyl, haloformyl, hydroxyl, aldehyde, formamide, amine, amino, alkoxy, azo, benzyl, carbonate, carboxylic acid ester, carboxyl, ketamine, isocyanate, isonitrile, isothiocyanate, nitrile, nitroso, phosphine, phosphate ester, phosphonyl, pyridyl, sulfonyl, sulfinyl, mercapto, halogen, aryl, substituted aryl, heteroaryl, substituted heteroaryl, heterocycle and its derivatives.

[0083] Those skilled in the art will understand that, where appropriate, the portion substituted on the hydrocarbon chain can itself be substituted. For example, substituents of the substituted alkyl group can include halogens, hydroxyl groups, nitro groups, thiols, amino groups, azides, imino groups, amide groups, phosphoryl groups (including phosphonates and phosphonites), sulfonyl groups (including sulfates, sulfonamides, aminosulfonyls, and sulfonates), and silyl groups, as well as ethers, alkylthio groups, carbonyl groups (including ketones, aldehydes, carboxylic acid esters, and esters), haloalkyl groups, -CN, etc. Cycloalkyl groups can be substituted in the same manner.

[0084] As used herein, “substituted” refers to all permitted substituents of the compounds or functional groups described herein. In the broadest sense, permitted substituents include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, aromatic and non-aromatic substituents of organic compounds. Exemplary substituents include, but are not limited to, halogens, hydroxyl groups, or any other organic combination containing any number of carbon atoms (preferably 1-14 carbon atoms) and optionally one or more heteroatoms (e.g., oxygen, sulfur, or nitrogen) in a linear, branched, or cyclic structural form. Representative substituents include alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, phenyl, substituted phenyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, halogen, hydroxyl, alkoxy, substituted alkoxy, phenoxy, substituted phenoxy, aryloxy, substituted aryloxy, alkylthio, substituted alkylthio, phenylthio, substituted phenylthio, arylthio, substituted arylthio, cyano, isocyano, substituted isocyano, oxo (=O), carbonyl, substituted carbonyl, carboxyl, substituted carboxyl, amino, substituted amino, amide, substituted amide, sulfonyl, substituted sulfonyl, sulfonic acid, phosphoryl, substituted phosphoryl, phosphonyl, substituted phosphonyl, polyaryl, substituted polyaryl, cyclic (e.g., C3-C) 20 Cyclic groups, substituted cyclic groups (such as substituted C3-C groups) 20Cyclic groups, heterocyclic groups, substituted heterocyclic groups, amino acids, poly(lactic-co-hydroxyacetic acid), peptides, polypeptides, deuterium, unsubstituted alkylynyl groups, substituted alkylynyl groups, unsubstituted arylynyl groups, substituted arylynyl groups, unsubstituted heteroarylynyl groups, substituted heteroarylynyl groups, trihaloalkyl (trifluoromethyl), unsubstituted heteroaryl ethers, substituted heteroaryl ethers, unsubstituted diarylamine groups, substituted diarylamine groups, unsubstituted dialkylamine groups, substituted... Dialkylamino, unsubstituted diarylamino, substituted diarylamino, unsubstituted diarylboraneyl, substituted diarylboraneyl, unsubstituted triarylsilyl, substituted triarylsilyl, unsubstituted trialkylsilyl, substituted trialkylsilyl, azo, carbonate, ketamine, nitro, nitroso, phosphinyl, pyridinyl, NRR', SR, C(O)R, COOR, C(O)NR, SOR, and BRR' groups, wherein R and R' are independently selected from hydrogen, deuterium, formaldehyde, cyano, alkylynyl, substituted alkylynyl, arylynyl, substituted arylynyl, heteroarylynyl, substituted heteroarylynyl, condensed polycyclic, substituted condensed polycyclic, aryl, alkyl, heteroaryl, nitro, trifluoromethane, cyano, aryl ether, alkyl ether, heteroaryl ether, diarylamine, dialkylamine, and diheteroarylamine. Diarylborane, triarylsilane, trialkylsilane, alkenyl, alkylaryl, cycloalkyl, haloformyl, hydroxyl, aldehyde, formamide, amine, amino, alkoxy, azo, benzyl, carbonate, carboxylic acid ester, carboxyl, ketamine, isocyanate, isonitrile, isothiocyanate, nitrile, nitroso, phosphine, phosphate ester, phosphonyl, pyridyl, sulfonyl, thio, sulfinyl, mercapto, halogen, aryl, substituted aryl, heteroaryl, substituted heteroaryl and heterocyclic groups. These include alkyl groups, substituted alkyl groups, alkenyl groups, substituted alkenyl groups, alkynyl groups, substituted alkynyl groups, phenyl groups, substituted phenyl groups, aryl groups, substituted aryl groups, heteroaryl groups, substituted heteroaryl groups, halogens, hydroxyl groups, alkoxy groups, substituted alkoxy groups, phenoxy groups, substituted phenoxy groups, aryloxy groups, substituted aryloxy groups, alkylthio groups, substituted alkylthio groups, phenylthio groups, substituted phenylthio groups, arylthio groups, substituted arylthio groups, cyano groups, isocyano groups, substituted isocyano groups, carbonyl groups, substituted carbonyl groups, carboxyl groups, substituted carboxyl groups, amino groups, substituted amino groups, amide groups, substituted amide groups, sulfonyl groups, substituted sulfonyl groups, sulfonic acids, phosphoryl groups, substituted phosphoryl groups, phosphonyl groups, substituted phosphonyl groups, polyaryl groups, substituted polyaryl groups, and cyclic groups (such as C3-C). 20 Cyclic groups, substituted cyclic groups (such as substituted C3-C groups) 20Cyclic groups, heterocyclic groups, substituted heterocyclic groups, amino acids, poly(lactic-co-hydroxyacetic acid), peptides, polypeptides, deuterium, unsubstituted alkylynyl, substituted alkylynyl, unsubstituted arylynyl, substituted arylynyl, unsubstituted heteroarylynyl, substituted heteroarylynyl, trihaloalkyl (trifluoromethyl), unsubstituted heteroaryl ether, substituted heteroaryl ether, unsubstituted diarylamine, substituted diarylamine, unsubstituted dialkylamine, substituted dialkylamine, unsubstituted diheteroarylamine, substituted diheteroarylamine, unsubstituted diarylboryl, substituted diarylboryl, unsubstituted triarylsilyl, substituted triarylsilyl, unsubstituted trialkylsilyl, substituted trialkylsilyl, azo, carbonate, ketamine, nitro, nitroso, phospholipids, phosphinyl, and pyridyl can be further substituted.

[0085] As used herein, the term "heteroatom" includes, but is not limited to, S, O, N, P, Se, Te, As, Sb, Bi, B, Si, Ge, Sn, and Pb. Heteroatoms (e.g., nitrogen) may have hydrogen substituents and / or any permitted substituents in the organic compounds described herein that satisfy the heteroatom valence. It should be understood that "substituted" or "substituted" includes the implicit conditions that such substitution meets the permitted valence of the substituted atom and the substituent, and that the substitution results in a stable compound, i.e., a compound that does not spontaneously undergo transformations (such as rearrangement, cyclization, elimination, etc.).

[0086] As used herein, the term "alkene" refers to a hydrocarbon group having, for example, 2 to 24 carbon atoms and containing at least one carbon-carbon double bond in its structural formula. Asymmetric structures, such as (AB)C=C(CD), are intended to include E and Z isomers. It can be presumed that an asymmetric alkene is present in the structural formulas described herein, or that this can be explicitly indicated by the bond symbol of the C atoms.

[0087] As used in this article, the term "alkynyl" refers to a hydrocarbon group having, for example, 2 to 24 carbon atoms and containing at least one carbon-carbon triple bond in its structural formula.

[0088] The term "aryl" as used in this article refers to any C5-C 26 Carbon-based aromatic groups, fused aromatic ring systems, fused heterocyclic systems, or biaromatic ring systems. The broad term "aryl" as used herein includes 5-, 6-, 7-, 8-, 9-, 10-, 14-, 18-, and 24-membered monocyclic aromatic groups, including but not limited to benzene, naphthalene, anthracene, phenanthrene, etc. Examples include pyrene, cycloalkenes, and arsenic. "Aryl" further includes polycyclic systems having two or more cyclic rings, wherein two or more carbons are shared by two adjacent rings (i.e., "fused rings"), wherein at least one ring is aromatic; for example, the other one or more cyclic rings may be cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, and / or heterocyclic. The aryl group may be substituted with one or more groups, including but not limited to alkyl, alkynyl, alkenyl, aryl, halides, nitro, amino, esters, ketones, aldehydes, hydroxyl, carboxylic acids, or alkoxy groups.

[0089] The term "substituted aryl" refers to an aryl group in which one or more hydrogen atoms on one or more aromatic rings are replaced by one or more substituents, including but not limited to halogens, azides, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, alkoxy, carbonyl (e.g., ketones, aldehydes, carboxyl, alkoxycarbonyl, formyl or acyl), silyl, ethers, esters, thiocarbonyl (e.g., thioesters, thioacetates or thiocarbamates), alkoxy, phosphoryl, phosphate, phosphonate, phosphonite, amino (or quaternized amino), amide, amidine, imine, cyano, nitro, azide, mercapto, imino, alkylthio, sulfate, sulfonate, aminosulfonyl, sulfonamide, sulfonyl, heterocyclic, alkylaryl, haloalkyl (e.g. CF3, -CH2-CF3, -CCl3), -CN, aryl, heteroaryl, and combinations thereof.

[0090] The terms "heterocyclic," "heterocyclic," and "heterocyclic group" are used interchangeably to refer to a monocyclic, bicyclic, or tricyclic cyclic group containing 3-14 ring atoms (preferably 5-6 ring atoms) linked by ring carbon or nitrogen atoms. The ring atoms consist of carbon and one to four heteroatoms, each heteroatom selected from non-peroxidized oxygen, sulfur, and N (Y), where Y is absent or is H, O, or Cl-C. 10 Alkyl, phenyl, or benzyl groups, optionally containing 1-3 double bonds and optionally substituted with one or more substituents. By definition, heterocyclic groups are different from heteroaryl groups. Examples of heterocycles include, but are not limited to: piperazinyl, piperidinyl, piperidinoneyl, 4-piperidinoneyl, dihydrofuran[2,3-b]tetrahydrofuran, morpholinyl, piperazinyl, piperidinyl, piperidinoneyl, 4-piperidinoneyl, piperinyl, piperanyl, 2H-pyrroleyl, 4H-quinazinyl, quinyl, tetrahydrofuranyl, 6H-1,2,5-thiadiazinyl. Heterocyclic groups may optionally be substituted with one or more alkyl and aryl substituents as defined above.

[0091] The term "heteroaryl" refers to C5-C 26A heteroaryl group is a monocyclic aromatic ring system, a fused aromatic ring system, a bicyclic aromatic ring system, or a combination thereof, wherein one or more carbon atoms in one or more aromatic ring structures are replaced by heteroatoms. Suitable heteroatoms include, but are not limited to, oxygen, sulfur, and nitrogen. The term "heteroaryl" as used herein broadly includes 5-, 6-, 7-, 8-, 9-, 10-, 14-, 18-, and 24-membered monocyclic aromatic groups, which may include one to four heteroatoms, such as pyrrole, furan, thiophene, imidazole, oxazole, thiazole, triazole, tetraazole, pyrazole, pyridine, pyrazine, pyridazine, and pyrimidine. Heteroaryl groups may also be referred to as "aryl heterocycles" or "heteroaromatic rings." "Heteroaryl" further includes polycyclic systems having two or more rings, wherein two or more carbons are shared by two adjacent rings (i.e., "fused rings"), wherein at least one ring is a heteroaromatic ring; for example, the other cyclic ring or rings may be cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, heterocyclic, or combinations thereof. Examples of heterocycles include, but are not limited to: benzimidazolyl, benzofuranyl, benzothiofuranyl, benzothiopheneyl, benzooxazolyl, benzooxazolinyl, benzothiazolyl, benzotriazolyl, benzotetrazoleyl, benzoisooxazolyl, benzoisothiazolyl, benzimidazolinyl, carbazoleyl, 4aH-carbazoleyl, carbolinyl, chromanyl, chromenyl, cenyl, decahydroquinolinyl, 2H,6H-1,5,2-dithiazinyl, furanyl, furazanyl, imidazoalkyl, imidazolinyl Imidazolyl, 1H-indazolyl, indolenyl, indololinyl, indolazinyl, indolyl, 3H-indolenyl, isatinoyl, isobenzofuranyl, isochoryl, isoindazolyl, isoindolinyl, isoindolenyl, isoquinolinyl, isothiazolyl, isoxazolyl, methylenedioxyphenyl, naphthidyl, octahydroisoquinolinyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, 1 2,5-Oxadiazolyl, 1,3,4-Oxadiazolyl, Oxazolyl, Oxazolyl, Hydroxyindolyl, Pyrimidinyl, Phenyridinyl, Phenyrazolinyl, Phenoxathinyl, Phenoxazinyl, Phtharazineyl, Pteridinyl, Purine, Pyrazinyl, Pyrazolylalkyl, Pyrazolinyl, Pyrazolyl, Pyridazinyl, Pyridoxazole, Pyridoimidazole, Pyridothiazazole, Pyridinyl, Pyridinyl The rings can be substituted with pyrimidinyl, pyrrolyl, pyrrolinyl, pyrroloyl, quinazolinyl, quinolinyl, quinoxalinyl, tetrahydroisoquinolinyl, tetrahydroquinolinyl, tetrazolyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,2,5-thiadiazolyl, 1,3,4-thiadiazolyl, thianyl, thienyl, thienothiazolyl, thienooxazolyl, thienoimidazolyl, thiophenyl, and xanthonyl. One or more rings may be substituted with "substituted heteroaryl" as defined below.

[0092] The term "substituted heteroaryl" refers to a heteroaryl group in which one or more hydrogen atoms on one or more heteroaryl rings are replaced by one or more substituents, including but not limited to halogens, azides, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, alkoxy, carbonyl (e.g., ketones, aldehydes, carboxyl, alkoxycarbonyl, formyl or acyl), silyl, ethers, esters, thiocarbonyl (e.g., thioesters, thioacetic acids or thiocarbamates), alkoxy, phosphoryl, phosphate, phosphonate, phosphonite, amino (or quaternized amino), amide, amidine, imine, cyano, nitro, azide, mercapto, imino, alkylthio, sulfate, sulfonate, aminosulfonyl, sulfonamide, sulfonyl, heterocyclic, alkylaryl, haloalkyl (e.g. CF3, -CH2-CF3, -CCl3), -CN, aryl, heteroaryl, and combinations thereof.

[0093] The term "substituted alkenyl" refers to an alkenyl moiety having one or more substituents that replace one or more hydrogen atoms on one or more carbon atoms of a hydrocarbon skeleton. These substituents include, but are not limited to: halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (e.g., carboxyl, alkoxycarbonyl, formyl, or acyl), silyl, ether, ester, thiocarbonyl (e.g., thioester, thioacetate, or thiocarbamate), alkoxy, phosphoryl, phosphate, phosphonate, phosphonite, amino (or quaternized amino), amide, amidine, imine, cyano, nitro, azide, mercapto, alkylthio, sulfate, sulfonate, aminosulfonyl, sulfonamide, sulfonyl, heterocyclic, alkylaryl, haloalkyl, -CN, aryl, heteroaryl, and combinations thereof.

[0094] The term "substituted alkyne" refers to an alkyne moiety having one or more substituents that replace one or more hydrogen atoms on one or more carbon atoms of the hydrocarbon skeleton. These substituents include, but are not limited to: halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (e.g., carboxyl, alkoxycarbonyl, formyl, or acyl), silyl, ether, ester, thiocarbonyl (e.g., thioester, thioacetate, or thiocarbamate), alkoxy, phosphoryl, phosphate, phosphonate, phosphonite, amino (or quaternized amino), amide, amidine, imine, cyano, nitro, azide, mercapto, alkylthio, sulfate, sulfonate, aminosulfonyl, sulfonamide, sulfonyl, heterocyclic, alkylaryl, haloalkyl, -CN, aryl, heteroaryl, and combinations thereof.

[0095] As used herein, the term "cycloalkyl" refers to a non-aromatic carbonyl ring consisting of at least three carbon atoms. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. The term "heterocyclic alkyl group" refers to a cycloalkyl group as defined above, wherein at least one carbon atom of the ring (e.g., but not limited to nitrogen, oxygen, sulfur, or phosphorus) is substituted with a heteroatom.

[0096] As used herein, the term "aralkyl" refers to an aryl group having an alkyl, ynyl, or alkenyl group as defined above attached to an aromatic group. An example of an aralkyl group is a benzyl group.

[0097] As used herein, the term "carbonyl group" is well-known in the art and includes those parts that can be represented by the following general formula:

[0098]

[0099] Wherein, X is a bond, or represents oxygen or sulfur, and R represents hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocyclic, substituted or unsubstituted alkylaryl, substituted or unsubstituted aralkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl, -(CH2). m -R”, or a pharmaceutically acceptable salt, where R' represents hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocyclic, substituted or unsubstituted alkylaryl, substituted or unsubstituted aralkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl or -(CH2). m -R”; R” represents a hydroxyl group, a substituted or unsubstituted carbonyl group, an aryl group, a cycloalkyl ring, a cycloalkenyl ring, a heterocyclic or polycyclic ring; and m is zero or an integer from 1 to 8. Where X is oxygen, and R is as defined above, this part is also called a carboxyl group. When X is oxygen and R is hydrogen, this formula represents 'carboxylic acid'. Where X is oxygen and R' is hydrogen, this formula represents 'formate'. Where X is oxygen and R or R' is not hydrogen, this formula represents 'ester'. Typically, where the oxygen atom in the above formula is replaced by a sulfur atom, this formula represents a 'thiocarbonyl' group. Where X is sulfur and R or R' is not hydrogen, this formula represents 'thioester'. Where X is sulfur and R is hydrogen, this formula represents 'thiocarboxylic acid'. Where X is sulfur and R' is hydrogen, this formula represents 'thioformate'. Where X is a bond and R is not hydrogen, this formula represents 'ketone'. In this formula, X represents a bond and R represents hydrogen, and the formula represents 'aldehyde'.

[0100] The term “substituted carbonyl” refers to a carbonyl group as defined above, wherein one or more hydrogen atoms in R, R', or the group to which the part is attached are independently substituted.

[0101]

[0102] These substituents include, but are not limited to: halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (e.g., carboxyl, alkoxycarbonyl, formyl or acyl), silyl, ether, ester, thiocarbonyl (e.g., thioester, thioacetate or thiocarbamate), alkoxy, phosphoryl, phosphate, phosphonate, phosphonite, amino (or quaternized amino), amide, amidine, imine, cyano, nitro, azide, mercapto, alkylthio, sulfate, sulfonate, aminosulfonyl, sulfonamide, sulfonyl, heterocyclic, alkylaryl, haloalkyl, -CN, aryl, heteroaryl, and combinations thereof.

[0103] The term "carboxyl group" is as defined in the above general formula.

[0104]

[0105] And by formula -R iv COOH is defined more specifically, where R iv It can be alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclic, alkylaryl, aralkyl, aryl, or heteroaryl. In preferred forms, the straight-chain or branched alkyl, alkenyl, and alkynyl groups have 30 or fewer carbon atoms on their backbone (e.g., the straight-chain alkyl group is C1-C1). 30 The branched alkyl group is C3-C 30 The straight-chain alkenyl and alkynyl groups are C2-C. 30 The branched alkenyl and alkynyl groups are C3-C. 30 Preferably, there are 20 or fewer, more preferably 15 or fewer, and most preferably 10 or fewer. Similarly, preferred cycloalkyl, heterocyclic, aryl, and heteroaryl groups have 3-10 carbon atoms in their ring structure, more preferably 5, 6, or 7 carbon atoms in their ring structure.

[0106] The term "substituted carboxyl group" refers to a carboxyl group as defined above, where R iv One or more hydrogen atoms are substituted. These substituents include, but are not limited to: halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (e.g., carboxyl, alkoxycarbonyl, formyl, or acyl), silyl, ether, ester, thiocarbonyl (e.g., thioester, thioacetate, or thiocarbamate), alkoxy, phosphoryl, phosphate, phosphonate, phosphonite, amino (or quaternized amino), amide, amidine, imine, cyano, nitro, azide, mercapto, alkylthio, sulfate, sulfonate, aminosulfonyl, sulfonamide, sulfonyl, heterocyclic, alkylaryl, haloalkyl, -CN, aryl, heteroaryl, and combinations thereof.

[0107] The term "phenoxy" is well-known and refers to the formula OR v The compound in which Rv It is (i.e., -O-C6H5). Those skilled in the art will know that phenoxy is a type of aryloxy group.

[0108] The term "substituted phenoxy" refers to a phenoxy group as defined above, having one or more hydrogen atoms on one or more carbons of its benzene ring. These substituents include, but are not limited to: halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (e.g., carboxyl, alkoxycarbonyl, formyl, or acyl), silyl, ether, ester, thiocarbonyl (e.g., thioester, thioacetate, or thiocarbamate), alkoxy, phosphoryl, phosphate, phosphonate, phosphonite, amino (or quaternized amino), amide, amidine, imine, cyano, nitro, azide, mercapto, alkylthio, sulfate, sulfonate, aminosulfonyl, sulfonamide, sulfonyl, heterocyclic, alkylaryl, haloalkyl, -CN, aryl, heteroaryl, and combinations thereof.

[0109] The terms “aryloxy” and “aryloxy” are used interchangeably herein and are represented by -O-aryl or -O-heteroaryl, where aryl and heteroaryl are as defined herein.

[0110] The terms “substituted aryloxy” and “substituted aryloxy” are used interchangeably herein to refer to a -O-aryl or -O-heteroaryl group having one or more substituents that replace one or more hydrogen atoms on one or more ring atoms of an aryl or heteroaryl group as defined herein. These substituents include, but are not limited to: halogens, azides, alkyl groups, aralkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, hydroxyl groups, carbonyl groups (e.g., carboxyl, alkoxycarbonyl, formyl, or acyl), silyl groups, ethers, esters, thiocarbonyl groups (e.g., thioesters, thioacetic acids, or thiocarbamates), alkoxy groups, phosphoryl groups, phosphate esters, phosphonates, phosphonites, amino (or quaternized amino), amide groups, amidine, imine, cyano, nitro, azide, mercapto, alkylthio, sulfate, sulfonate, aminosulfonyl, sulfonamide, sulfonyl, heterocyclic, alkylaryl, haloalkyl, -CN, aryl, heteroaryl, and combinations thereof.

[0111] The term "alkathio" refers to an alkyl group as defined above, with a sulfide group attached thereto. The "alkathio" part is represented by -S-alkyl. Representative alkathio groups include methylthio and ethylthio. The term "alkathio" also includes cycloalkyl groups with a sulfide group attached thereto.

[0112] The term "substituted alkithio" refers to an alkithio group having one or more substituents that replace one or more hydrogen atoms on one or more carbon atoms of the alkithio skeleton. These substituents include, but are not limited to: halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (e.g., carboxyl, alkoxycarbonyl, formyl, or acyl), silyl, ether, ester, thiocarbonyl (e.g., thioester, thioacetate, or thiocarbamate), alkoxy, phosphoryl, phosphate, phosphonate, phosphonite, amino (or quaternized amino), amide, amidine, imine, cyano, nitro, azide, mercapto, alkithio, sulfate, sulfonate, aminosulfonyl, sulfonamide, sulfonyl, heterocyclic, alkylaryl, haloalkyl, -CN, aryl, heteroaryl, and combinations thereof.

[0113] The term "phenylthio" is well known in the art and refers to -S-C6H5, i.e., a phenyl group attached to a sulfur atom.

[0114] The term "substituted phenylthio" refers to a phenylthio group as defined above, having one or more substituents that replace hydrogen on one or more carbons of its benzene ring. These substituents include, but are not limited to: halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (e.g., carboxyl, alkoxycarbonyl, formyl, or acyl), silyl, ether, ester, thiocarbonyl (e.g., thioester, thioacetate, or thiocarbamate), alkoxy, phosphoryl, phosphate, phosphonate, phosphonite, amino (or quaternized amino), amide, amidine, imine, cyano, nitro, azide, mercapto, alkylthio, sulfate, sulfonate, aminosulfonyl, sulfonamide, sulfonyl, heterocyclic, alkylaryl, haloalkyl, -CN, aryl, heteroaryl, and combinations thereof.

[0115] "Arylthio" refers to -S-aryl or -S-heteroaryl groups, where aryl and heteroaryl are as defined herein.

[0116] The term "substituted arylthio" refers to a -S-aryl or -S-heteroaryl group having one or more substituents that replace one or more hydrogen atoms on the aryl and heteroaryl rings as defined herein. These substituents include, but are not limited to: halogens, azides, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (e.g., carboxyl, alkoxycarbonyl, formyl, or acyl), silyl, ethers, esters, thiocarbonyl (e.g., thioesters, thioacetic acids, or thiocarbamates), alkoxy, phosphoryl, phosphate, phosphonate, phosphonite, amino (or quaternized amino), amide, amidine, imine, cyano, nitro, azide, mercapto, alkylthio, sulfate, sulfonate, aminosulfonyl, sulfonamide, sulfonyl, heterocyclic, alkylaryl, haloalkyl, -CN, aryl, heteroaryl, and combinations thereof.

[0117] The terms "amide" or "amide group" are used interchangeably to refer to "unsubstituted amide group" and "substituted amide group," and are represented by the following general formula:

[0118]

[0119] Wherein, E is absent, or E is a substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aralkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted heterocyclic group, wherein independently of E, R and R' each independently represent hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted carbonyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocyclic group, substituted or unsubstituted alkylaryl, substituted or unsubstituted aralkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl, -(CH2). m -R”', or R and R' together with the N atom they are attached to form a heterocycle having 3 to 14 atoms in the ring structure; R”' represents a hydroxyl group, a substituted or unsubstituted carbonyl group, an aryl group, a cycloalkyl ring, a cycloalkenyl ring, a heterocycle, or a polycyclic ring; and m is zero or an integer from 1 to 8. In a preferred form, only one of R and R' can be a carbonyl group; for example, R and R' do not form a diimide with nitrogen. In a preferred form, R and R' each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or -(CH2). m -R”'. When E is oxygen, a carbamate is formed. As will be understood by those skilled in the art, a carbamate cannot be linked to another chemical species, such as to form an oxygen-oxygen bond or other unstable bonds.

[0120] The term "sulfonyl" is represented by the following formula.

[0121]

[0122] Where E is absent, or E is alkyl, alkenyl, alkynyl, aralkyl, alkylaryl, cycloalkyl, aryl, heteroaryl, or heterocyclic, wherein, independent of E, R represents hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted amine, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocyclic, substituted or unsubstituted alkylaryl, substituted or unsubstituted aralkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl, -(CH2). m-R”', or E and R together with the S atom they are attached to form a heterocycle having 3 to 14 atoms in the ring structure; R”' represents a hydroxyl group, a substituted or unsubstituted carbonyl group, an aryl group, a cycloalkyl ring, a cycloalkenyl ring, a heterocycle, or a polycyclic ring; and m is zero or an integer from 1 to 8. In the preferred form, only one of E and R can be a substituted or unsubstituted amine to form a "sulfonamide" or "sulfonamide group". Substituted or unsubstituted amines are as defined above.

[0123] The term "substituted sulfonyl" refers to a sulfonyl group in which E, R, or both are independently substituted. These substituents include, but are not limited to: halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (e.g., carboxyl, alkoxycarbonyl, formyl, or acyl), silyl, ether, ester, thiocarbonyl (e.g., thioester, thioacetate, or thiocarbamate), alkoxy, phosphoryl, phosphate, phosphonate, phosphonite, amino (or quaternized amino), amide, amidine, imine, cyano, nitro, azide, mercapto, alkylthio, sulfate, sulfonate, aminosulfonyl, sulfonamide, sulfonyl, heterocyclic, alkylaryl, haloalkyl, -CN, aryl, heteroaryl, and combinations thereof.

[0124] The term "sulfonic acid" refers to a sulfonyl group as defined above, wherein R is a hydroxyl group and E is absent, or E is a substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocyclic, substituted or unsubstituted alkylaryl, substituted or unsubstituted aralkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.

[0125] The term "sulfate ester" refers to a sulfonyl group as defined above, wherein E is non-oxygen, oxygen, alkoxy, aryloxy, a substituted alkoxy or a substituted aryloxy group as defined above, and R is independently a hydroxyl, alkoxy, aryloxy, a substituted alkoxy or a substituted aryloxy group as defined above. As will be understood by those skilled in the art, when E is oxygen, a sulfate ester cannot be linked to another chemical species, such as forming an oxygen-oxygen bond or other unstable bonds.

[0126] The term "sulfonate" refers to a sulfonyl group as defined above, wherein E is oxygen, alkoxy, aryloxy, a substituted alkoxy or substituted aryloxy group as defined above, and R is independently hydrogen, a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted amine, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted heterocyclic, a substituted or unsubstituted alkylaryl, a substituted or unsubstituted aralkyl, a substituted or unsubstituted aryl, or a substituted or unsubstituted heteroaryl, -(CH2). m-R”', where R”' represents a hydroxyl group, a substituted or unsubstituted carbonyl group, an aryl group, a cycloalkyl ring, a cycloalkenyl ring, a heterocyclic or polycyclic ring, and m is zero or an integer from 1 to 8. As will be understood by those skilled in the art, when E is oxygen, sulfonates cannot be linked to another chemical species, such as to form an oxygen-oxygen bond or other unstable bonds.

[0127] The term "aminosulfonyl" refers to sulfonamides or sulfonamides represented by the following formula.

[0128]

[0129] Where E is absent, or E is a substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aralkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted heterocyclic, wherein independently of E, R and R' each independently represent hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted carbonyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocyclic, substituted or unsubstituted alkylaryl, substituted or unsubstituted aralkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl, -(CH2). m -R”', or R and R' together with the N atom to which they are attached, form a heterocycle having 3 to 14 atoms in the ring structure; R”' represents a hydroxyl group, a substituted or unsubstituted carbonyl group, an aryl group, a cycloalkyl ring, a cycloalkenyl ring, a heterocycle, or a polycyclic ring; and m is zero or an integer from 1 to 8. In a preferred form, only one of R and R' can be a carbonyl group; for example, R and R' do not form a diimide with nitrogen.

[0130] The term "phosphonoyl" is represented by the following formula.

[0131]

[0132] Where E is absent, or E is a substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aralkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted heterocyclic, wherein independent of E, R vi and R vii Independently, it is hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted carbonyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocyclic, substituted or unsubstituted alkylaryl, substituted or unsubstituted aralkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl, -(CH2). m-R”', or R and R' together with the P atoms they are attached to form a heterocycle with 3 to 14 atoms in the ring structure; R”' represents a hydroxyl group, a substituted or unsubstituted carbonyl group, an aryl group, a cycloalkyl ring, a cycloalkenyl ring, a heterocycle or a polycyclic ring; and m is zero or an integer from 1 to 8.

[0133] The term "substituted phosphonoyl group" indicates that E and R are substituted. vi and R vii Independently substituted phosphonoyl groups. These substituents include, but are not limited to: halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (e.g., carboxyl, alkoxycarbonyl, formyl, or acyl), silyl, ether, ester, thiocarbonyl (e.g., thioester, thioacetate, or thiocarbamate), alkoxy, phosphoryl, phosphate, phosphonate, phosphonite, amino (or quaternized amino), amide, amidine, imine, cyano, nitro, azide, mercapto, alkylthio, sulfate, sulfonate, aminosulfonyl, sulfonamide, sulfonyl, heterocyclic, alkylaryl, haloalkyl, -CN, aryl, heteroaryl, and combinations thereof.

[0134] The term "phosphonyl" defines a phosphonyl group, wherein E is non-oxygen, oxygen, alkoxy, aryloxy, substituted alkoxy or substituted aryloxy as defined above, and R is independent of E. vi and R vii Independently, it can be a hydroxyl, alkoxy, aryloxy, substituted alkoxy, or substituted aryloxy group as defined above. As will be understood by those skilled in the art, when E is oxygen, the phosphoryl group cannot be linked to another chemical species, such as forming an oxygen-oxygen bond or other unstable bonds. When E, R... vi and R vii When substituted, the substituents include, but are not limited to, halogens, azides, alkyl groups, aralkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, hydroxyl groups, carbonyl groups (e.g., carboxyl, alkoxycarbonyl, formyl, or acyl), silyl groups, ethers, esters, thiocarbonyl groups (e.g., thioesters, thioacetic esters, or thiocarbamates), alkoxy groups, phosphoryl groups, phosphate esters, phosphonates, phosphonites, amino (or quaternized amino), amide groups, amidine, imine, cyano, nitro, azide, mercapto, alkylthio, sulfate esters, sulfonates, aminosulfonyl, sulfonamide, sulfonyl, heterocyclic, alkylaryl, haloalkyl, -CN, aryl, heteroaryl, and combinations thereof.

[0135] The term "polyaryl" refers to a chemical moiety comprising two or more aryl, heteroaryl, and combinations thereof. Aryl, heteroaryl, and combinations thereof are fused or linked by single bonds, ethers, esters, carbonyl groups, amides, sulfonyl groups, sulfonamides, alkyl groups, azo groups, and combinations thereof. When two or more heteroaryl groups are involved, the chemical moiety may be referred to as "polyheteroaryl".

[0136] The term "substituted polyaryl" refers to a polyaryl group in which one or more aryl or heteroaryl groups are replaced by one or more substituents, including but not limited to halogens, azides, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (e.g., carboxyl, alkoxycarbonyl, formyl, or acyl), silyl, ether, ester, thiocarbonyl (e.g., thioester, thioacetate, or thiocarbamate), alkoxy, phosphoryl, phosphate, phosphonate, phosphonite, amino (or quaternized amino), amide, amidine, imine, cyano, nitro, azide, mercapto, alkylthio, sulfate, sulfonate, aminosulfonyl, sulfonamide, sulfonyl, heterocyclic, alkylaryl, haloalkyl, -CN, aryl, heteroaryl, and combinations thereof. When two or more heteroaryl groups are involved, the chemical motif may be referred to as "substituted polyheteroaryl".

[0137] The term "cycle" refers to a substituted or unsubstituted cycloalkyl, substituted or unsubstituted cycloalkenyl, substituted or unsubstituted cycloynyl, or substituted or unsubstituted heterocyclic group, preferably having 3 to 20 carbon atoms where geometric conditions permit. The ring structure is formed by a single or fused ring system. The substituted cycloalkyl, cycloalkenyl, cycloynyl, and heterocyclic groups are the substitutions of alkyl, alkenyl, ynyl, and heterocyclic groups as defined above, respectively.

[0138] II. Composition

[0139] This document describes a two-coordinate d10 metal carbene complex containing an imidazopyrazine ligand (e.g., a pyrazine-fused N-heterocyclic carbene (NHC) ligand), an imidazopyridine ligand (e.g., a pyridine-fused NHC), or a pyrrolopyrazine ligand (e.g., a pyrazine-fused NHC). The radiometric properties of the compound can be controlled by TADF. Preferably, the d10 metal carbene complex comprises a d10 metal (such as Cu(I), Ag(I), or Au(I)) in the +1 oxidation state, a pyrazine-fused NHC ligand, and a carbazole ligand. Preferred pyrazine-fused NHC ligands or pyridine-fused N-heterocyclic carbene ligands comprise a 2,6-diisopropylphenyl group covalently bonded to the nitrogen atom of the imidazolium moiety of the pyrazine-fused NHC ligand. The compound (i) is easy to mass-produce, (ii) has lower production costs due to the abundance of metal (copper) on Earth, (iii) exhibits tunable emission characteristics, such as from blue-green to orange-red, (iv) is sublimable and solution-processable for OLED manufacturing, (v) shows improved OLED brightness and efficiency compared to existing emitters, and / or (vi) shows improved device stability compared to reported d10 Cu / Ag / Au emitters.

[0140] The compounds of this invention have the following structures:

[0141]

[0142] in:

[0143] The compound is generally neutral, negatively charged, or positively charged.

[0144] M is copper, silver, or gold, with an oxidation state of 0, +1, +2, or +3, preferably +1.

[0145] P' has the following structure:

[0146]

[0147] D represents carbon.

[0148] T, J, and W are independently carbon or nitrogen, wherein at least one of T, J, and W is nitrogen, wherein J is nitrogen when T is carbon, or J is carbon when T is nitrogen, and T, J, and W are bonded to a hydrogen atom or not bonded to a hydrogen atom depending on their valence.

[0149] X and Y are independently carbon or nitrogen, wherein at least one of X and Y is nitrogen, and X and Y are bonded to a hydrogen atom or not bonded to a hydrogen atom depending on their valence.

[0150] R1 and R2 are independently hydrogen, substituted alkyl, unsubstituted alkyl, substituted alkenyl, unsubstituted alkenyl, substituted alkynyl, unsubstituted alkynyl, substituted aryl, unsubstituted aryl, halogen, hydroxyl, thiol, cyano, nitro, unsubstituted alkoxy, substituted alkoxy, unsubstituted aryloxy, substituted aryloxy, unsubstituted heteroaryl, substituted heteroaryl, unsubstituted polyheteroaryl, substituted polyheteroaryl, unsubstituted alkathiol, substituted alkathiol, unsubstituted carbonyl, substituted carbonyl, unsubstituted carboxyl, substituted carboxyl, unsubstituted ester, substituted ester, substituted C3-C 20 cycloalkyl, unsubstituted C3-C 20 cycloalkyl, substituted C2-C 20 Heterocyclic group, unsubstituted C2-C 20 Heterocyclic groups, substituted C3-C 20 Cycloalkenyl, unsubstituted C3-C 20 Cycloalkenyl, substituted C3-C 20 Cycloynyl or unsubstituted C3-C 20 Cycloalkynyl, or R1, J, D and R2 together forming an unsubstituted aryl, substituted aryl, unsubstituted heteroaryl or substituted heteroaryl,

[0151] R3 and R4 are independently hydrogen, substituted alkenyl, unsubstituted alkenyl, substituted alkynyl, unsubstituted alkynyl, substituted aryl, unsubstituted aryl, halogen, hydroxyl, thiol, cyano, nitro, unsubstituted alkoxy, substituted alkoxy, unsubstituted aryloxy, substituted aryloxy, unsubstituted heteroaryl, substituted heteroaryl, unsubstituted polyheteroaryl, substituted polyheteroaryl, unsubstituted alkylthio, substituted alkylthio, unsubstituted carbonyl, substituted carbonyl, unsubstituted carboxyl, substituted carboxyl, unsubstituted ester, substituted ester, substituted C3-C 20 cycloalkyl, unsubstituted C3-C 20 cycloalkyl, substituted C2-C 20 Heterocyclic group, unsubstituted C2-C 20 Heterocyclic groups, substituted C3-C 20 Cycloalkenyl, unsubstituted C3-C 20 Cycloalkenyl,

[0152] R3' and R4' are independently non-hydrogen, substituted alkyl, unsubstituted alkyl, substituted alkenyl, unsubstituted alkenyl, substituted alkynyl, unsubstituted alkynyl, substituted aryl, unsubstituted aryl, halogen, hydroxyl, thiol, cyano, nitro, unsubstituted alkoxy, substituted alkoxy, unsubstituted aryloxy, substituted aryloxy, unsubstituted heteroaryl, substituted heteroaryl, unsubstituted polyheteroaryl, substituted polyheteroaryl, unsubstituted alkathio, substituted alkathio, unsubstituted carbonyl, substituted carbonyl, unsubstituted carboxyl, substituted carboxyl, unsubstituted ester, substituted ester, substituted C3-C 20 cycloalkyl, unsubstituted C3-C 20 cycloalkyl, substituted C2-C 20 Heterocyclic group, unsubstituted C2-C 20 Heterocyclic groups, substituted C3-C 20 Cycloalkenyl, unsubstituted C3-C 20 Cycloalkenyl, substituted C3-C 20 Cycloynyl or unsubstituted C3-C 20 Cycloacetylenic, and

[0153] Z represents a substituted heteroaryl group, an unsubstituted heteroaryl group, a substituted polyheteroaryl group, an unsubstituted polyheteroaryl group, a substituted polyheterocyclic group, an unsubstituted polyheterocyclic group, a substituted heterocyclic group, or an unsubstituted heterocyclic group, or -NR. a R b , where R a and R b Independently hydrogen, substituted aryl, unsubstituted aryl, substituted heteroaryl, unsubstituted heteroaryl, substituted C3-C 20 cycloalkyl, unsubstituted C3-C 20Cycloalkyl, substituted heterocyclic, unsubstituted heterocyclic, substituted alkyl or unsubstituted alkyl,

[0154] Wherein (i) R3 and R4 are not simultaneously 3,5-dialkyl-substituted aryl groups, (ii) R3 and R4 are not simultaneously 3,5-dialkyl-substituted phenyl groups, (iii) R3 and R4 are not simultaneously 3,5-dimethylphenyl groups, (iv) when M is Cu or Au, R3 and R4 are not simultaneously 3,5-dimethylphenyl groups, or (v) the compound is not...

[0155]

[0156] In some forms, the compounds of the present invention are as described in Formula I above, except that the compounds have the following structure:

[0157]

[0158] CY1 and CY2 are independently substituted aryl, unsubstituted aryl, substituted polyaryl, unsubstituted polyaryl, substituted heteroaryl, unsubstituted heteroaryl, substituted polyheteroaryl, unsubstituted polyheteroaryl, and substituted C3-C. 20 cycloalkyl, unsubstituted C3-C 20 cycloalkyl, substituted C3-C 20 Cycloalkenyl, unsubstituted C3-C 20 Cycloalkenyl, substituted C3-C 20 Cycloynyl or unsubstituted C3-C 20 Cycloalkynyl. In some forms, CY1 and CY2 are independently substituted aryl, unsubstituted aryl, substituted polyaryl, or unsubstituted polyaryl. In some forms, CY1 and CY2 are substituted aryl.

[0159] In some forms, the compounds of the present invention are as described in Formula I or Formula II above, except that R3' and R4' are absent.

[0160] In some forms, the compounds of the present invention are as described in Formula I or Formula II above, except that the compounds have the following structure:

[0161]

[0162] in:

[0163] R5 and R6 are independently substituted or unsubstituted alkyl groups, and

[0164] n1 and n2 are independent integers between 0 and 5, 1 and 5, 2 and 5 (e.g., 2), or 3 and 5 (e.g., 3).

[0165] In some forms, the compounds of the present invention are as described in any one of formulas I-III above, except that the compound has the following structure:

[0166]

[0167] in:

[0168] n1 and n2 are independent integers between 1 and 5, 2 and 5, or 3 and 5.

[0169] L represents an alkyl group without a single bond, a substituted alkyl group, or -(CH2). nx - Ox, sulfur, or NRx, wherein nx is an integer between 1 and 3 (e.g., 1, 2, or 3), and Rx is an unsubstituted alkyl, a substituted alkyl, an unsubstituted aryl, or a substituted aryl, and

[0170] CY3 and CY4 are independently unsubstituted aryl, substituted aryl, unsubstituted polyaryl, substituted polyaryl, unsubstituted heteroaryl, substituted heteroaryl, unsubstituted polyheteroaryl, substituted polyheteroaryl, and unsubstituted C3-C. 20 cycloalkyl, substituted C3-C 20 cycloalkyl, substituted C3-C 20 Cycloalkenyl, unsubstituted C3-C 20 Cycloalkenyl, substituted C3-C 20 Cycloalkynyl, unsubstituted C3-C 20 Cycloalynyl or a combination thereof.

[0171] In some forms, the compounds of the present invention are as described in any one of formulas I-IV above, except that the compound has the following structure:

[0172]

[0173] in:

[0174] Each Ra is independently hydrogen, an unsubstituted alkyl group, or a substituted alkyl group.

[0175] Each Rb is independently an unsubstituted alkyl or a substituted alkyl.

[0176] L represents an alkyl group without a single bond, a substituted alkyl group, or -(CH2). nx - Ox, sulfur, or NRx, wherein nx is an integer between 1 and 3 (e.g., 1, 2, or 3), and Rx is an unsubstituted alkyl, substituted alkyl, unsubstituted aryl, or substituted aryl, and optionally, wherein at least one of X and Y is nitrogen. In some forms, X and Y are nitrogen.

[0177] In some forms, the compounds of the present invention are as described in any of Formula IV above, except that:

[0178] (i) T represents nitrogen, J represents carbon, and W represents carbon.

[0179] (ii) T represents nitrogen, J represents carbon, and W represents nitrogen.

[0180] (iii) T is carbon, J is nitrogen, and W is carbon, or

[0181] (iv) T represents carbon, J represents nitrogen, and W represents nitrogen.

[0182] In some forms, the compounds of the present invention are as described in Formula V above, except that Ra is hydrogen, an unsubstituted alkyl or a substituted alkyl, and Rb is an unsubstituted alkyl or a substituted alkyl.

[0183] In some forms, the compounds of the present invention are as described in any of Formula IV above, except that P' is selected from:

[0184]

[0185] in:

[0186] Ra is hydrogen, an unsubstituted alkyl group, or a substituted alkyl group, and

[0187] Rb is an unsubstituted alkyl group or a substituted alkyl group.

[0188] In some forms, the compounds of the present invention are as described in any of Formula IV above, wherein, when specified in detail, Ra is hydrogen, methyl, isopropyl or -CH(C2H5)2, and Rb is methyl, isopropyl or -CH(C2H5)2.

[0189] In some forms, the compounds of the present invention are as described in Formula IV or Formula V above, except that CY3 and CY4 are independently unsubstituted aryl, substituted aryl, unsubstituted polyaryl, substituted polyaryl, unsubstituted heteroaryl, substituted heteroaryl, or substituted C3-C 20 Cycloalkenyl, unsubstituted C3-C 20 Cycloalkenyl groups or combinations thereof. In some forms, CY3 and CY4 are independently unsubstituted aryl, substituted aryl, unsubstituted heteroaryl, substituted heteroaryl, or substituted C3-C. 20 Cycloalkenyl, unsubstituted C3-C 20 Cycloalkenyl groups or combinations thereof.

[0190] In some forms, the compounds of the present invention are as described in any of Formula IV above, except that Z has the following structure:

[0191]

[0192] in:

[0193] X1, X2, X3, X4, X5, X6, X7, and X8 are independently carbon or nitrogen.

[0194] Rx1, Rx2, Rx3, Rx4, Rx5, Rx6, Rx7, and Rx8 are independently hydrogen, halogen, cyano, unsubstituted alkyl, substituted alkyl, unsubstituted alkoxy, substituted alkoxy, unsubstituted aryl, substituted aryl, unsubstituted heteroaryl, or substituted heteroaryl, wherein when the corresponding X1, X2, X3, X4, X5, X6, X7, or X8 is nitrogen, each Rx1, Rx2, Rx3, Rx4, Rx5, Rx6, Rx7, or Rx8 is absent, or Rx4 is a bonded to a substituent on L, or the adjacent Rxn groups, together with the atoms in the ring to which they are bonded, independently collectively form a five- or six-membered substituted aryl, unsubstituted aryl, substituted heteroaryl, unsubstituted heteroaryl, or substituted C3-C group. 20 Cycloalkenyl, unsubstituted C3-C 20 Cycloalkenyl groups or combinations thereof, wherein n in adjacent Rxn groups is a consecutive integer pair of 1 to 4 or 5 to 8, and

[0195] L represents an alkyl group without a single bond, a substituted alkyl group, or -(CH2). nx - Ox, sulfur, or NRx, wherein nx is an integer between 1 and 3 (e.g., 1, 2, or 3), and Rx is an unsubstituted alkyl, a substituted alkyl, an unsubstituted aryl, or a substituted aryl.

[0196] In some forms, the compounds of the present invention are as described in any of Formula IV above, except that Z has the following structure:

[0197]

[0198] in:

[0199] L' is a substituted aryl group, an unsubstituted aryl group, a substituted heteroaryl group, or an unsubstituted heteroaryl group, preferably a substituted aryl group or an unsubstituted aryl group, preferably a substituted phenyl group or an unsubstituted phenyl group.

[0200] In some forms, the compounds of the present invention are as described in any of Formula IV above, except that Z has the following structure:

[0201]

[0202] in:

[0203] X1, X2, X3, X4, X5, X6, X7, and X8 are independently carbon or nitrogen, and

[0204] Rx1, Rx2, Rx3, Rx4, Rx5, Rx6, Rx7, and Rx8 are independently hydrogen, halogen, cyano, unsubstituted alkyl, substituted alkyl, unsubstituted alkoxy, substituted alkoxy, unsubstituted aryl, substituted aryl, unsubstituted heteroaryl, or substituted heteroaryl, wherein when the corresponding X1, X2, X3, X4, X5, X6, X7, or X8 is nitrogen, each Rx1, Rx2, Rx3, Rx4, Rx5, Rx6, Rx7, or Rx8 is absent, or the adjacent Rxn groups, together with the atoms in the ring to which they are bonded, independently and collectively form a five- or six-membered substituted aryl, unsubstituted aryl, substituted heteroaryl, unsubstituted heteroaryl, or substituted C3-C group. 20 Cycloalkenyl, unsubstituted C3-C 20 Cycloalkenyl groups or combinations thereof, wherein n in adjacent Rxn groups is a consecutive integer pair of 1 to 4 or 5 to 8.

[0205] In some forms, the compound is as described in any of the formulas I to V above, wherein, when specified in detail, Rx1, Rx2, Rx3, Rx4, Rx5, Rx6, Rx7 and Rx8 are independently hydrogen, halogen, methyl, cyano, trifluoromethyl, tert-butyl, methoxy, phenyl or pyridyl.

[0206] In some forms, the compounds of the present invention are as described in any of Formula IV above, except that the compound has the following structure:

[0207] Preferred

[0208] in:

[0209] "V" represents carbon.

[0210] U is carbon and V is nitrogen, or U is nitrogen and V is carbon, where U, V, and V are bonded to or not bonded to a hydrogen atom depending on their valence.

[0211] Ra is hydrogen, an unsubstituted alkyl group, or a substituted alkyl group.

[0212] R7 and R8 are independently unsubstituted, hydrogen-free, substituted alkyl, unsubstituted alkyl, cyano, halogen, hydroxyl, thiol, nitro, unsubstituted alkoxy, substituted alkoxy, unsubstituted aryloxy, substituted aryloxy, substituted aryl, unsubstituted aryl, or adjacent R7 or adjacent R8 groups, together with atoms in the ring they are bonded to, independently form a five- or six-membered substituted aryl, unsubstituted aryl, substituted heteroaryl, unsubstituted heteroaryl, or substituted C3-C group. 20 Cycloalkenyl, unsubstituted C3-C 20 Cycloalkenyl groups or combinations thereof, and

[0213] n3 and n4 are independent integers between 0 and 5, such as 0, 1, 2, 3, 4, 5.

[0214] In some forms, the compounds of the present invention are as described in Formula VI above, except that the compounds have the following structure:

[0215] Preferred

[0216] in:

[0217] Rv is an unsubstituted, hydrogen-free, substituted, or unsubstituted alkyl group, and

[0218] R7 and R8 are independently hydrogen, substituted alkyl, unsubstituted alkyl, unsubstituted aryl, halogen, cyano, or

[0219] Rv and R7, together with the atoms in the rings they are bonded to, form five- or six-membered substituted aryl groups, unsubstituted aryl groups, substituted heteroaryl groups, unsubstituted heteroaryl groups, and substituted C3-C groups. 20 Cycloalkenyl, unsubstituted C3-C 20 Cycloalkenyl groups or combinations thereof.

[0220] In some forms, the compounds of the present invention are as described in Formula VI or Formula VII above, except that:

[0221] Rv is either absent or hydrogen.

[0222] R7 and R8 are independently hydrogen, isopropyl, tert-butyl, phenyl, fluorine, or cyano, or

[0223] Rv and R7 together form

[0224]

[0225] In some forms, the compounds of the present invention are as described in any of formulas I-VII above, except that R1 and R2 are independently hydrogen, substituted alkyl, unsubstituted alkyl, substituted alkenyl, unsubstituted alkenyl, substituted alkynyl, unsubstituted alkynyl, substituted aryl, unsubstituted aryl, or R1 and R2 together with atoms in the ring to which they are bonded form an unsubstituted aryl, substituted aryl, unsubstituted heteroaryl, or substituted heteroaryl. In some forms, R1 and R2 are hydrogen. In some forms, R1 and R2 together form the following structure:

[0226]

[0227] In some forms, the compounds of the present invention are as described in any one of formulas I-VII above, except that the compound has the following structure:

[0228] Preferred

[0229] in:

[0230] (i) M=Cu(I); W=N; Ra=H; U=CH; V=V"=carbon; Rv=H; R7=R8=H;

[0231] (ii) M=Cu(I); W=N; Ra=H; U=CH; V=V"=carbon; Rv=H; R7=H; R8=CN;

[0232] (iii) M = Cu(I); W = N; Ra = H; U = CH; V = V" = carbon; Rv = H; R7 = R8 = tert-butyl;

[0233] (iv) M = Cu(I); W = N; Ra = H; U = CH; V = V" = carbon; Rv = H; R7 = R8 = phenyl;

[0234] (v)M=Cu(I); W=N; Ra=H; U=CH; V=N; V″=carbon; Rv=None; R7=R8=H;

[0235] (vi) M = Cu(I); W = U = CH; V = V" = carbon; Rv = H; Ra = isopropyl; R7 = R8 = H;

[0236] (vii) M = Cu(I); W = N; Ra = H; U = CH; V = V" = carbon; R8 = H; Rv and R7 form together.

[0237]

[0238] (viii) M = Cu(I); W = U = CH; Ra = isopropyl; V = V" = carbon; R8 = H; Rv and R7 form together

[0239]

[0240] (ix) M=Cu(I); W=N; Ra=H; U=CH; V=V"=carbon; Rv=H; R7=R8=H;

[0241] (x)M=Cu(I); W=N; Ra=H; U=CH; V=V"=carbon; Rv=H; R7=H; R8=F;

[0242] (xi)M=Cu(I); W=N; Ra=H; U=CH; V=V"=carbon; Rv=H; R7=R8=methyl;

[0243] (xii) M=Au(I); W=N; Ra=H; U=CH; V=carbon; Rv=H; V"=carbon; R7=R8=H;

[0244] (xiii) M = Au(I); W = N; Ra = H; U = CH; V = carbon; Rv = H; V" = carbon; R7 = H; R8 = CN;

[0245] (xiv)M=Au(I);W=N;Ra=H;U=N;V=carbon;Rv=H;V"=carbon;R7=R8=H;

[0246] (xv)M=Au(I);W=U=CH;V=carbon;Rv=H;Ra=isopropyl;V"=carbon;R7=R8=H;

[0247] (xvi)M=Au(I);W=N;Ra=H;U=CH;V=N;Rv=none;V"=carbon;R7=R8=H;

[0248] (xvii) M=Au(I); W=N; Ra=H; U=CH; V=V"=carbon; Rv=H; R7=R8=CN;

[0249] (xviii) M = Au(I); W = N; Ra = hydrogen; U = CH; V = V" = carbon; R8 = H; Rv and R7 form together

[0250]

[0251] (xix)M=Au(I); W=U=CH; Ra=isopropyl; V=V"=carbon; Rv=H; R7=R8=tert-butyl;

[0252] (xx)M=Au(I);W=U=CH;Ra=isopropyl;V=V"=carbon;Rv=H;R7=H;R8=F;

[0253] (xxi)M=Au(I); W=N; U=CH; Ra=H; V=V"=carbon; Rv=H; R7=R8=H;

[0254] (xxii)M=Au(I);W=N;U=CH;Ra=H;V=V"=carbon;Rv=H;R7=R8=tert-butyl;

[0255] (xxiii) M=Ag(I); W=N; U=CH; Ra=H; V=V"=carbon; Rv=H; R7=R8=H;

[0256] For (i), (ii), (iii), (iv), (v), (vi), (vii), (viii), (xii), (xiii), (xiv), (xv), (xvi), (xvii), (xviii), (xix), (xx), and (xxiii), the dashed lines indicate no key, and

[0257] For (ix), (x), (xi), (xxi), and (xxii), the dashed lines indicate the presence of a bond.

[0258] In some forms, the compounds of the present invention are selected from the following structures:

[0259]

[0260]

[0261]

[0262] Where M = Cu(I), Au(I), or Ag(I).

[0263] In some forms, the compounds of the present invention are as described in any of formulas I-VII above, except that substitution refers to being substituted by one or more substituents selected from: halogen, hydroxyl, thiol, nitro, unsubstituted alkyl, unsubstituted alkenyl, unsubstituted alkynyl, unsubstituted aryl, unsubstituted heteroaryl, unsubstituted aralkyl, unsubstituted alkoxy, unsubstituted aryloxy, unsubstituted alkylthio, unsubstituted arylthio, cyano, isocyano, unsubstituted carbonyl, unsubstituted carboxyl, oxo (=O), unsubstituted amino, unsubstituted amide, unsubstituted sulfonyl, unsubstituted sulfonic acid, unsubstituted phosphoryl, unsubstituted phosphonyl, unsubstituted polyaryl, or unsubstituted C3-C. 20 Cycloalkyl groups, and unsubstituted heterocyclic groups.

[0264] In some forms, the compounds of the present invention have a photoluminescence quantum yield (PLQY) between 0.50 and 0.95, for example, between 0.58 and 0.92 in thin films. In some forms, the compounds of the present invention have an emission decay lifetime (τ) in thin films between 0.20 μs and 0.45 μs, for example, between 0.23 μs and 42 μs. In some forms, the compounds of the present invention have a PLQY between 0.50 and 0.95 (e.g., between 0.58 and 0.92) and an emission decay lifetime (τ) between 0.20 μs and 0.45 μs (e.g., between 0.23 μs and 42 μs) in thin films. In some forms, the radiative rate constant of the compounds of the present invention in thin films is in the range of 10⁻³⁵ × 10⁻³⁵. 5 s -1 Between, for example, 15-21×105 s -1 Or ~29×10 5 s -1 The film may also contain organic compounds. Exemplary organic compounds include, but are not limited to, host materials such as 1,3-bis(N-carbazolyl)benzene (mCP), 2,8-bis(diphenylphospho)dibenzo[b,d]furan (PPF), bis[2-(diphenylphospho)phenyl]ether oxide (DPEPO), 3,3'-bis(9H-carbazol-9-yl)-1,1'-biphenyl (mCBP), polymethyl methacrylate (PMMA), polystyrene (PS), or combinations thereof.

[0265] In some forms, the compounds of the present invention act as sensitizers to transfer energy (e.g., exciton energy or photon energy) to a purely organic emitter. In some forms, the compounds of the present invention act as sensitizers to transfer energy (e.g., exciton energy or photon energy) to a purely organic emitter exhibiting thermally activated delayed fluorescence. In some forms, the compounds of the present invention act as sensitizers to transfer energy (e.g., exciton energy or photon energy) to a boron-based purely organic emitter. The phrase "pure organic emitter" as used throughout this application refers to a luminescent organic molecule composed solely of main group elements of the periodic table, such that the luminescent organic molecule does not contain covalent bonds or coordinate bonds with main group metals. It is important to note that this phrase is not intended to define or specify the purity level of compositions containing luminescent organic molecules.

[0266] Each compound defined above is intended and should be considered as specifically disclosed herein. Furthermore, each subgroup identifiable in the above definitions is intended and should be considered as specifically disclosed herein. Therefore, any compound or subgroup of compounds specifically considered may be specifically included or excluded from use, or included in or excluded from the list of compounds. For example, any one or more compounds described herein, having the structure described herein, or mentioned in the tables or examples herein, may be specifically included, excluded, or combined in any combination of groups or subgroups of these compounds. These specific groups, subgroups, inclusions, and exclusions may apply to any aspect of the compositions and methods described herein. For example, a group of compounds that specifically excludes one or more specific compounds may be used or applied in the content of a compound itself (e.g., a series or group of compounds), a composition comprising that compound (e.g., a pharmaceutical composition), any one or more disclosed methods, or a combination of these methods. Different groups and subgroups of compounds having such specific inclusions and exclusions may be used or applied in the content of a compound itself, a composition comprising one or more compounds, or any disclosed method. All these different groups and subgroups of compounds—as well as different groups of compounds, compositions and methods of using or applying these compounds—are specifically and individually considered and should be considered specifically and individually described.

[0267] III. Preparation methods and reagents

[0268] A. Compound

[0269] The dicoordinated d10 metal carbene complexes and their ligands described herein can be synthesized using methods known in the field of organic chemical synthesis. The target compound can be synthesized by reacting a corresponding pyrazine-fused NHC ligand, a corresponding pyrazine-fused NHC ligand precursor, or a combination thereof with a d10 compound in a solvent or solution to form a complex precursor. Exemplary solvents include organic solvents such as tetrahydrofuran and dichloromethane. The complex precursor can be reacted with a second ligand (e.g., carbazole) for a suitable time to form the d10 metal carbene complex. Specific d10 metal carbene complexes, such as those containing Cu(I), Ag(I), and Au(I), are disclosed in the examples.

[0270] B. Organic light-emitting devices

[0271] Methods for manufacturing organic light-emitting devices (e.g., OLEDs) comprising one or more d10 metal carbene complexes of any one of formulas I-VIII described above are also described. Preferred methods for manufacturing OLEDs include vacuum deposition or solution processing techniques, such as spin coating and ink printing (e.g., inkjet printing or roll-to-roll printing). An embodiment discloses a method for manufacturing an OLED comprising the d10 metal carbene complexes described herein.

[0272] IV. Instructions for Use

[0273] Preferably, the d10 metal carbene complexes described herein are photostable and emissive at room temperature, low temperature, or a combination thereof. Accordingly, the compounds described herein can be used in OLEDs, organic photovoltaic cells (OPVs), and organic field-effect transistors (OFETs) or light-emitting electrochemical cells (LEECs), and in fixed visual display units, mobile visual display units, or lighting devices. Examples of units or devices include commercial products such as smartphones, televisions, monitors, digital cameras, tablets, keyboards, clothing accessories, garment trims, wearable devices, medical monitoring devices, wallpaper, advertising panels, laptops, home appliances, office supplies, and lighting fixtures. Preferably, these units or devices are those that typically operate at room temperature.

[0274] In some forms, the compound may be contained within the emissive layer. In some forms, one or more compounds may be contained within the emissive layer containing a purely organic emitter, such that the one or more compounds act as sensitizers to transfer energy (e.g., exciton energy or photon energy) to the purely organic emitter. In some forms, one or more compounds have singlet states at higher positions than the purely organic emitter. In some forms, the purely organic emitter exhibits thermally activated delayed fluorescence. In some forms, the purely organic emitter is boron-based. In some forms, the emissive layer may be contained within the OLED.

[0275] The disclosed compounds, methods of use, and methods of preparation can be further understood through the following paragraphs or embodiments.

[0276] 1. A compound having the following structure:

[0277]

[0278] in:

[0279] The compound is generally neutral, negatively charged, or positively charged.

[0280] M is copper, silver, or gold, with an oxidation state of 0, +1, +2, or +3, preferably +1.

[0281] P' has the following structure:

[0282]

[0283] D represents carbon.

[0284] T, J, and W are independently carbon or nitrogen, wherein at least one of T, J, and W is nitrogen, wherein J is nitrogen when T is carbon, or J is carbon when T is nitrogen, and T, J, and W are bonded to a hydrogen atom or not bonded to a hydrogen atom depending on their valence.

[0285] X and Y are independently carbon or nitrogen, with at least one of X and Y being nitrogen, and X and Y being bonded to a hydrogen atom or not bonded to a hydrogen atom depending on their valence.

[0286] R1 and R2 are independently hydrogen, substituted alkyl, unsubstituted alkyl, substituted alkenyl, unsubstituted alkenyl, substituted alkynyl, unsubstituted alkynyl, substituted aryl, unsubstituted aryl, halogen, hydroxyl, thiol, cyano, nitro, unsubstituted alkoxy, substituted alkoxy, unsubstituted aryloxy, substituted aryloxy, unsubstituted heteroaryl, substituted heteroaryl, unsubstituted polyheteroaryl, substituted polyheteroaryl, unsubstituted alkathiol, substituted alkathiol, unsubstituted carbonyl, substituted carbonyl, unsubstituted carboxyl, substituted carboxyl, unsubstituted ester, substituted ester, substituted C3-C 20 cycloalkyl, unsubstituted C3-C 20 cycloalkyl, substituted C2-C 20 Heterocyclic group, unsubstituted C2-C 20 Heterocyclic groups, substituted C3-C 20 Cycloalkenyl, unsubstituted C3-C 20 Cycloalkenyl, substituted C3-C 20 Cycloynyl or unsubstituted C3-C 20 Cycloalkynyl, or R1, J, D and R2 together forming an unsubstituted aryl, substituted aryl, unsubstituted heteroaryl or substituted heteroaryl,

[0287] R3 and R4 are independently hydrogen, substituted alkenyl, unsubstituted alkenyl, substituted alkynyl, unsubstituted alkynyl, substituted aryl, unsubstituted aryl, halogen, hydroxyl, thiol, cyano, nitro, unsubstituted alkoxy, substituted alkoxy, unsubstituted aryloxy, substituted aryloxy, unsubstituted heteroaryl, substituted heteroaryl, unsubstituted polyheteroaryl, substituted polyheteroaryl, unsubstituted alkylthio, substituted alkylthio, unsubstituted carbonyl, substituted carbonyl, unsubstituted carboxyl, substituted carboxyl, unsubstituted ester, substituted ester, substituted C3-C 20 cycloalkyl, unsubstituted C3-C 20 cycloalkyl, substituted C2-C 20 Heterocyclic group, unsubstituted C2-C 20 Heterocyclic groups, substituted C3-C20 Cycloalkenyl, unsubstituted C3-C 20 Cycloalkenyl, substituted C3-C 20 Cycloynyl, or unsubstituted C3-C 20 Cycloacetylenic group.

[0288] R3' and R4' are independently non-hydrogen, substituted alkyl, unsubstituted alkyl, substituted alkenyl, unsubstituted alkenyl, substituted alkynyl, unsubstituted alkynyl, substituted aryl, unsubstituted aryl, halogen, hydroxyl, thiol, cyano, nitro, unsubstituted alkoxy, substituted alkoxy, unsubstituted aryloxy, substituted aryloxy, unsubstituted heteroaryl, substituted heteroaryl, unsubstituted polyheteroaryl, substituted polyheteroaryl, unsubstituted alkathio, substituted alkathio, unsubstituted carbonyl, substituted carbonyl, unsubstituted carboxyl, substituted carboxyl, unsubstituted ester, substituted ester, substituted C3-C 20 cycloalkyl, unsubstituted C3-C 20 cycloalkyl, substituted C2-C 20 Heterocyclic group, unsubstituted C2-C 20 Heterocyclic groups, substituted C3-C 20 Cycloalkenyl, unsubstituted C3-C 20 Cycloalkenyl, substituted C3-C 20 Cycloynyl, or unsubstituted C3-C 20 Cycloacetylenic, and

[0289] Z represents a substituted heteroaryl group, an unsubstituted heteroaryl group, a substituted polyheteroaryl group, an unsubstituted polyheteroaryl group, a substituted polyheterocyclic group, an unsubstituted polyheterocyclic group, a substituted heterocyclic group, or an unsubstituted heterocyclic group, or -NR. a R b , where R a and R b Independently hydrogen, substituted aryl, unsubstituted aryl, substituted heteroaryl, unsubstituted heteroaryl, substituted C3-C 20 cycloalkyl, unsubstituted C3-C 20 Cycloalkyl, substituted heterocyclic, unsubstituted heterocyclic, substituted alkyl or unsubstituted alkyl,

[0290] Wherein (i) R3 and R4 are not simultaneously 3,5-dialkyl-substituted aryl groups, (ii) R3 and R4 are not simultaneously 3,5-dialkyl-substituted phenyl groups, (iii) R3 and R4 are not simultaneously 3,5-dimethylphenyl groups, (iv) when M is Cu or Au, R3 and R4 are not simultaneously 3,5-dimethylphenyl groups, or (v) the compound is not...

[0291]

[0292] 2. The compound in paragraph 1 has the following structure:

[0293]

[0294] CY1 and CY2 are independently substituted aryl, unsubstituted aryl, substituted polyaryl, unsubstituted polyaryl, substituted heteroaryl, unsubstituted heteroaryl, substituted polyheteroaryl, unsubstituted polyheteroaryl, and substituted C3-C. 20 cycloalkyl, unsubstituted C3-C 20 cycloalkyl, substituted C3-C 20 Cycloalkenyl, unsubstituted C3-C 20 Cycloalkenyl, substituted C3-C 20 Cycloynyl or unsubstituted C3-C 20 Cycloacetic group.

[0295] 3. The compounds in paragraphs 1 or 2, wherein R3' and R4' are absent.

[0296] 4. The compound of paragraph 2 or 3, wherein CY1 and CY2 are independently substituted aryl, unsubstituted aryl, substituted polyaryl, or unsubstituted polyaryl.

[0297] 5. Any compound in paragraphs 2 to 4, wherein CY1 and CY2 are substituted aryl groups.

[0298] 6. Any of the compounds in paragraphs 1 to 5, having the following structure:

[0299]

[0300] in:

[0301] R5 and R6 are independently substituted or unsubstituted alkyl groups, and

[0302] n1 and n2 are independent integers between 0 and 5, between 1 and 5, between 3 and 5 (e.g., 3), or between 2 and 5 (e.g., 2).

[0303] 7. Any of the compounds in paragraphs 1 to 6, having the following structure:

[0304]

[0305] in:

[0306] n1 and n2 are independent integers between 1 and 5, 2 and 5, or 3 and 5.

[0307] L represents an alkyl group without a single bond, a substituted alkyl group, or -(CH2). nx- Ox, sulfur, or NRx, wherein nx is an integer between 1 and 3 (e.g., 1, 2, or 3), and Rx is an unsubstituted alkyl, a substituted alkyl, an unsubstituted aryl, or a substituted aryl, and

[0308] CY3 and CY4 are independently unsubstituted aryl, substituted aryl, unsubstituted polyaryl, substituted polyaryl, unsubstituted heteroaryl, substituted heteroaryl, unsubstituted polyheteroaryl, substituted polyheteroaryl, and unsubstituted C3-C. 20 cycloalkyl, substituted C3-C 20 cycloalkyl, substituted C3-C 20 Cycloalkenyl, unsubstituted C3-C 20 Cycloalkenyl, substituted C3-C 20 Cycloalkynyl, unsubstituted C3-C 20 Cycloalynyl or a combination thereof.

[0309] 8. The compound described in any one of paragraphs 1 to 7 has the following structure:

[0310]

[0311] in:

[0312] Each Ra is independently hydrogen, an unsubstituted alkyl group, or a substituted alkyl group.

[0313] Each Rb is independently an unsubstituted alkyl or a substituted alkyl.

[0314] L represents an alkyl group without a single bond, a substituted alkyl group, or -(CH2). nx - Ox, sulfur, or NRx, wherein nx is an integer between 1 and 3 (e.g., 1, 2, or 3), and Rx is an unsubstituted alkyl, a substituted alkyl, an unsubstituted aryl, or a substituted aryl, and

[0315] Optionally, at least one of X and Y is nitrogen.

[0316] 9. Any of the compounds in paragraphs 1 through 8, wherein:

[0317] (i) T represents nitrogen, J represents carbon, and W represents carbon.

[0318] (ii) T represents nitrogen, J represents carbon, and W represents nitrogen.

[0319] (iii) T is carbon, J is nitrogen, and W is carbon, or

[0320] (iv) T represents carbon, J represents nitrogen, and W represents nitrogen.

[0321] 10. The compounds in paragraphs 8 or 9, wherein:

[0322] Ra is independently hydrogen, an unsubstituted alkyl group, or a substituted alkyl group, and

[0323] Rb is independently an unsubstituted alkyl or a substituted alkyl.

[0324] 11. Any compound from paragraphs 1 to 10, wherein P' is selected from:

[0325]

[0326] in:

[0327] Ra is independently hydrogen, an unsubstituted alkyl group, or a substituted alkyl group, and

[0328] Rb is independently an unsubstituted alkyl or a substituted alkyl.

[0329] 12. Any of the compounds in paragraphs 8 to 11, wherein:

[0330] Ra can be independently hydrogen, methyl, isopropyl, or -CH(C2H5)2, and

[0331] Rb can be methyl, isopropyl, or -CH(C2H5)2 independently.

[0332] 13. Any compound in paragraphs 7 to 12, wherein CY3 and CY4 are independently unsubstituted aryl, substituted aryl, unsubstituted polyaryl, substituted polyaryl, unsubstituted heteroaryl, substituted heteroaryl, or substituted C3-C. 20 Cycloalkenyl, unsubstituted C3-C 20 Cycloalkenyl groups or their fused combinations.

[0333] 14. Any compound in paragraphs 7 to 13, wherein CY3 and CY4 are independently unsubstituted aryl, substituted aryl, unsubstituted heteroaryl, substituted heteroaryl, or substituted C3-C 20 Cycloalkenyl, unsubstituted C3-C 20 Cycloalkenyl groups or combinations thereof.

[0334] 15. Any of the compounds in paragraphs 1 to 14, wherein Z has the following structure:

[0335]

[0336] in:

[0337] X1, X2, X3, X4, X5, X6, X7, and X8 are independently carbon or nitrogen.

[0338] Rx1, Rx2, Rx3, Rx4, Rx5, Rx6, Rx7, and Rx8 are independently hydrogen, halogen, cyano, unsubstituted alkyl, substituted alkyl, unsubstituted alkoxy, substituted alkoxy, unsubstituted aryl, substituted aryl, unsubstituted heteroaryl, or substituted heteroaryl, wherein when the corresponding X1, X2, X3, X4, X5, X6, X7, or X8 is nitrogen, each Rx1, Rx2, Rx3, Rx4, Rx5, Rx6, Rx7, or Rx8 is absent, or Rx4 is a bonded to a substituent on L, or the adjacent Rxn groups, together with the atoms in the ring to which they are bonded, independently collectively form a five- or six-membered substituted aryl, unsubstituted aryl, substituted heteroaryl, unsubstituted heteroaryl, or substituted C3-C group. 20 Cycloalkenyl, unsubstituted C3-C 20 Cycloalkenyl groups or combinations thereof, wherein n in adjacent Rxn groups is a consecutive integer pair of 1 to 4 or 5 to 8, and

[0339] L represents an alkyl group without a single bond, a substituted alkyl group, or -(CH2). nx - Ox, sulfur, or NRx, wherein nx is an integer between 1 and 3 (e.g., 1, 2, or 3), and Rx is an unsubstituted alkyl, a substituted alkyl, an unsubstituted aryl, or a substituted aryl.

[0340] 16. Any of the compounds in paragraphs 1 to 15, wherein Z has the following structure:

[0341]

[0342] in:

[0343] L' is a substituted aryl group, an unsubstituted aryl group, a substituted heteroaryl group, or an unsubstituted heteroaryl group, preferably a substituted aryl group or an unsubstituted aryl group, preferably a substituted phenyl group or an unsubstituted phenyl group.

[0344] 17. The compound of paragraph 15, wherein Z has the following structure:

[0345]

[0346] 18. The compounds of paragraph 15 or 17, wherein Rx1, Rx2, Rx3, Rx4, Rx5, Rx6, Rx7 and Rx8 are independently hydrogen, halogen, methyl, cyano, trifluoromethyl, tert-butyl, methoxy, phenyl or pyridyl.

[0347] 19. Any of the compounds in paragraphs 1 to 18, wherein X and Y are nitrogen.

[0348] 20. The compound in paragraph 1 has the following structure:

[0349] Preferred

[0350] in:

[0351] "V" represents carbon.

[0352] U is carbon and V is nitrogen, or U is nitrogen and V is carbon, where U, V, and V are bonded to or not bonded to a hydrogen atom depending on their valence.

[0353] Ra is hydrogen, an unsubstituted alkyl group, or a substituted alkyl group.

[0354] R7 and R8 are independently unsubstituted, hydrogen-free, substituted alkyl, unsubstituted alkyl, cyano, halogen, hydroxyl, thiol, nitro, unsubstituted alkoxy, substituted alkoxy, unsubstituted aryloxy, substituted aryloxy, substituted aryl, unsubstituted aryl, or adjacent R7 or adjacent R8 groups, together with atoms in the ring they are bonded to, independently form a five- or six-membered substituted aryl, unsubstituted aryl, substituted heteroaryl, unsubstituted heteroaryl, or substituted C3-C group. 20 Cycloalkenyl, unsubstituted C3-C 20 Cycloalkenyl groups or combinations thereof, and

[0355] n3 and n4 are independent integers between 0 and 5, such as 0, 1, 2, 3, 4, 5.

[0356] 21. The compound in paragraph 19 has the following structure:

[0357] Preferred

[0358] in:

[0359] Rv is an unsubstituted, hydrogen-free, substituted, or unsubstituted alkyl group, and

[0360] R7 and R8 are independently hydrogen, substituted alkyl, unsubstituted alkyl, unsubstituted aryl, halogen, or cyano, or

[0361] Rv and R7, together with the atoms in the rings they are bonded to, form five- or six-membered substituted aryl groups, unsubstituted aryl groups, substituted heteroaryl groups, unsubstituted heteroaryl groups, and substituted C3-C groups. 20 Cycloalkenyl, unsubstituted C3-C 20 Cycloalkenyl groups or combinations thereof.

[0362] 22. The compounds in paragraphs 20 or 21, wherein:

[0363] Rv is either absent or hydrogen.

[0364] R7 and R8 are independently hydrogen, isopropyl, tert-butyl, phenyl, fluorine, or cyano, or

[0365] Rv and R7 together form

[0366]

[0367] 23. Any of the compounds in paragraphs 20 to 22, wherein:

[0368] R1 and R2 are independently hydrogen, substituted alkyl, unsubstituted alkyl, substituted alkenyl, unsubstituted alkenyl, substituted ynyl, unsubstituted ynyl, substituted aryl, unsubstituted aryl, or

[0369] R1 and R2 together with the atoms in the ring to which they are bonded form unsubstituted aryl, substituted aryl, unsubstituted heteroaryl, or substituted heteroaryl.

[0370] 24. Any of the compounds in paragraphs 20 to 23, wherein:

[0371] R1 and R2 are hydrogen, or

[0372] R1 and R2 together form the following structure:

[0373]

[0374] 25. The compound in paragraph 24 has the following structure:

[0375] Preferred

[0376] in:

[0377] (i) M=Cu(I); W=N; Ra=H; U=CH; V=V"=carbon; Rv=H; R7=R8=H;

[0378] (ii) M=Cu(I); W=N; Ra=H; U=CH; V=V"=carbon; Rv=H; R7=H; R8=CN;

[0379] (iii) M = Cu(I); W = N; Ra = H; U = CH; V = V" = carbon; Rv = H; R7 = R8 = tert-butyl;

[0380] (iv) M = Cu(I); W = N; Ra = H; U = CH; V = V" = carbon; Rv = H; R7 = R8 = phenyl;

[0381] (v)M=Cu(I); W=N; Ra=H; U=CH; V=N; V"=carbon; Rv=None; R7=R8=H;

[0382] (vi) M = Cu(I); W = U = CH; V = V" = carbon; Rv = H; Ra = isopropyl; R7 = R8 = H;

[0383] (vii) M = Cu(I); W = N; Ra = H; U = CH; V = V" = carbon; R8 = H; Rv and R7 form together.

[0384]

[0385] (viii) M = Cu(I); W = U = CH; Ra = isopropyl; V = V" = carbon; R8 = H; Rv and R7 form together

[0386]

[0387] (ix) M=Cu(I); W=N; Ra=H; U=CH; V=V"=carbon; Rv=H; R7=R8=H;

[0388] (x)M=Cu(I); W=N; Ra=H; U=CH; V=V"=carbon; Rv=H; R7=H; R8=F;

[0389] (xi)M=Cu(I); W=N; Ra=H; U=CH; V=V"=carbon; Rv=H; R7=R8=methyl;

[0390] (xii) M=Au(I); W=N; Ra=H; U=CH; V=carbon; Rv=H; V"=carbon; R7=R8=H;

[0391] (xiii) M = Au(I); W = N; Ra = H; U = CH; V = carbon; Rv = H; V" = carbon; R7 = H; R8 = CN;

[0392] (xiv)M=Au(I);W=N;Ra=H;U=N;V=carbon;Rv=H;V"=carbon;R7=R8=H;

[0393] (xv)M=Au(I);W=U=CH;V=carbon;Rv=H;Ra=isopropyl;V"=carbon;R7=R8=H;

[0394] (xvi)M=Au(I);W=N;Ra=H;U=CH;V=N;Rv=none;V"=carbon;R7=R8=H;

[0395] (xvii) M=Au(I); W=N; Ra=H; U=CH; V=V"=carbon; Rv=H; R7=R8=CN;

[0396] (xviii) M = Au(I); W = N; Ra = hydrogen; U = CH; V = V" = carbon; R8 = H; Rv and R7 form together

[0397]

[0398] (xix)M=Au(I); W=U=CH; Ra=isopropyl; V=V"=carbon; Rv=H; R7=R8=tert-butyl;

[0399] (xx)M=Au(I);W=U=CH;Ra=isopropyl;V=V"=carbon;Rv=H;R7=H;R8=F;

[0400] (xxi)M=Au(I); W=N; U=CH; Ra=H; V=V"=carbon; Rv=H; R7=R8=H;

[0401] (xxii)M=Au(I);W=N;U=CH;Ra=H;V=V"=carbon;Rv=H;R7=R8=tert-butyl;

[0402] (xxiii) M=Ag(I); W=N; U=CH; Ra=H; V=V"=carbon; Rv=H; R7=R8=H;

[0403] For (i), (ii), (iii), (iv), (v), (vi), (vii), (viii), (xii), (xiii), (xiv), (xv), (xvi), (xvii), (xviii), (xix), (xx), and (xxiii), the dashed lines indicate no key, and

[0404] For (ix), (x), (xi), (xxi), and (xxii), the dashed lines indicate the presence of a bond.

[0405] 26. The compound in paragraph 1 has the following structure:

[0406]

[0407]

[0408]

[0409] Where M = Cu(I), Au(I), or Ag(I).

[0410] 27. Any compound in paragraphs 1 to 25, wherein substitution means being substituted by one or more substituents selected from: halogen, hydroxyl, thiol, nitro, unsubstituted alkyl, unsubstituted alkenyl, unsubstituted alkynyl, unsubstituted aryl, unsubstituted heteroaryl, unsubstituted aralkyl, unsubstituted alkoxy, unsubstituted aryloxy, unsubstituted alkylthio, unsubstituted arylthio, cyano, isocyano, unsubstituted carbonyl, unsubstituted carboxyl, oxo, unsubstituted amino, unsubstituted amide, unsubstituted sulfonyl, unsubstituted sulfonic acid, unsubstituted phosphoryl, unsubstituted phosphonyl, unsubstituted polyaryl, or unsubstituted C3-C 20 Cycloalkyl groups, and unsubstituted heterocyclic groups.

[0411] 28. An organic electronic component comprising any of the compounds in paragraphs 1 to 27.

[0412] 29. Organic electronic components in paragraph 28, wherein the organic electronic components are organic light-emitting diodes (OLEDs) or light-emitting electrochemical cells (LEECs).

[0413] 30. Organic electronic components in paragraphs 28 or 29, wherein the compound is in the light-emitting layer.

[0414] 31. Any organic electronic component in paragraphs 28 to 30 further includes an anode, a cathode, a hole transport region, and an electron transport region.

[0415] The hole transport region includes a hole injection layer and / or a hole transport layer, and optionally an electron blocking layer.

[0416] The electron transport region includes an electron transport layer and / or an electron injection layer, and optionally a hole blocking layer.

[0417] The light-emitting layer is located between the anode and the cathode.

[0418] The hole transport region is located between the anode and the light-emitting layer, and the electron transport region is located between the cathode and the light-emitting layer.

[0419] 32. Organic electronic components of paragraphs 29 or 30, wherein the light-emitting layer is manufactured by vacuum deposition, spin coating, or ink printing (e.g., inkjet printing or roll-to-roll printing).

[0420] 33. A light-emitting layer comprising any of the compounds in paragraphs 1 to 27.

[0421] 34. A light-emitting layer comprising a compound of any one of paragraphs 1 to 27 and a pure organic light emitter, wherein the compound acts as a sensitizer to transfer energy (e.g., exciton energy or photon energy) to the pure organic light emitter.

[0422] 35. A light-emitting layer comprising any one of the compounds in paragraphs 1 to 27 and a pure organic light emitter, wherein the compound has a higher singlet state than the pure organic light emitter.

[0423] 36. A light-emitting layer comprising any one of the compounds in paragraphs 1 to 27 and a pure organic light emitter, wherein the compound acts as a sensitizer to transfer energy (e.g., exciton energy or photon energy) to the pure organic emitter exhibiting thermally activated delayed fluorescence.

[0424] 37. A light-emitting layer comprising a compound of any one of paragraphs 1 to 27 and a pure organic light emitter, wherein the compound acts as a sensitizer to transfer energy (e.g., exciton energy or photon energy) to the boron-based pure organic emitter.

[0425] 38. An OLED comprising an emissive layer of any one of paragraphs 33 to 37.

[0426] 39. An OLED comprising segment 38, wherein the device is selected from fixed visual display units, mobile visual display units, lighting units, keyboards, clothing, decorations, garment accessories, wearable devices, medical monitoring devices, wallpaper, tablet computers, laptop computers, advertising panels, panel display units, home appliances, or office supplies.

[0427] Example

[0428] Several d10 metal (Cu(I), Ag(I), or Au(I)) carbene complexes composed of pyrazine-fused N-heterocyclic carbene (NHC) ligands and carbazole derivatives were prepared. These complexes exhibited highly efficient photoluminescence quantum yields (0.58–0.92) and short emission decay lifetimes (0.23–0.42 μs) in 1,3-bis(N-carbazolyl)benzene (mCP) films, demonstrating efficient photoluminescence quantum yields (TADF). The radiative decay rate constants of these complexes were very high, with the Cu(I) complex exhibiting 15–21 × 10⁻⁶. 5 s -1 k r The Au(I) complex has a strength of ~29 × 10⁻⁶. 5 s -1 k r Both are higher than previously reported Cu(I)(k) compounds composed of cyclic (alkyl) (amino)carbenes (CAAC) (Nature Communications 2020, 11, 1758; Chem. Sci. 2020, 11, 435), monoamide-aminocarbenes (MAC*) (J. Am. Chem. Soc. 2019, 141, 3576-3588), or diamide carbenes (DAC*) (J. Am. Chem. Soc. 2019, 141, 3576-3588). r0.38-10×10 5 s -1 ) and Au(I)(0.53-22×10 5 s -1 The counterpart of ).

[0429] It is believed that the improved properties of the disclosed d10 metal carbene complexes are achieved through the use of pyrazine-fused or pyridine-fused NHC ligands modified with bulky 2,6-diisopropylphenyl (DIPP) side groups in these dicoordinated d10 metal carbene complexes. This ligand structure increases chemical and electrochemical stability, improving electroluminescence performance and photoluminescence quantum yield by suppressing excited-state structural distortion. This electroluminescence performance (i.e., ultra-high device brightness and significantly long device lifetime) is unprecedented for d10 emitters. Furthermore, the emission color of such emitters can be tuned by using carbazole derivatives with different donor strengths. For example, green (Cu2 and Au2), yellow (Cu1, Au1, and Ag1), and red (Cu3) emitters have been prepared.

[0430] Example 1: Synthesis and Characterization of Compounds

[0431] Materials and methods

[0432] The chemical reagents used in the synthesis were purchased from commercial sources such as Dieckmann, Tiv Scientific, J&K Scientific, BLDpharm, and Bidepharm. They were used directly without further processing. The solvents used in the synthesis were purchased from Duksan, RCI Labscan, and Scharlau. They were used directly without further processing.

[0433] (i) Synthesis of pyrazine-fused or pyridine-fused N-heterocyclic carbene ligands

[0434] process Figure 1 The synthesis of pyrazine-fused NHC ligands is shown.

[0435]

[0436] (a) Synthesis of N,N'-bis(2,6-diisopropylphenyl)pyrazine-2,3-diamine

[0437] In a sealed tube, 2,6-diisopropylaniline (3.0 eq.) was added to a 1 M solution of hexamethyldisilyl lithium azide (LiHMDS) in THF (3.5 eq.). The resulting mixture was stirred under argon atmosphere for 30 min. Then, 2,3-dichloropyrazine (1.0 eq.) was added to the reaction mixture and heated overnight at 80 °C. After the reaction, the solvent was evaporated to dryness, the residue was extracted with DCM, and then purified by column chromatography. 1 H NMR (500MHz, CDCl3) δ / ppm 7.49 (s, 1H), 7.34–7.30 (m, 1H), 7.24 (d, J = 7.6Hz, 2H), 5.72 (s, 1H), 3.10 (dt, J = 13.5, 6.7Hz, 2H), 1.19 (d, J = 6.7Hz, 16H). 13 C NMR (100MHz, CDCl3) δ / ppm 146.10, 144.34, 133.84, 132.40, 127.98, 124.03, 28.98, 23.88. HRESI-MS[M+H] + For [C] 28 H 38 N4] + Calculated m / z value: 431.3169, measured value: 431.3168.

[0438] (b) Synthesis of 1,3-bis(2,6-diisopropylphenyl)imidazo[4,5-b]pyrazine-3-chloroiumonium (PzIm-Cl)

[0439] A solution of N,N'-bis(2,6-diisopropylphenyl)pyrazine-2,3-diamine (1.2 mmol) in triethyl orthoformate was added to a round-bottom flask. The mixture was heated at 150 °C for 6 hours. The mixture was then cooled to room temperature and excess trimethylchlorosilane was added. The resulting reaction mixture was heated at 70 °C overnight. After the reaction was complete, the precipitate was collected by filtration, washed with Et₂O, and dried in air to give a grayish-white solid. 1 HNMR (500MHz, CDCl3) δ / ppm 13.64 (br s, 1H), 8.87 (s, 2H), 7.66 (t, J = 7.5Hz, 2H), 7.42 (d, J = 8.0Hz, 4H), 2.99 (m, 4H), 1.30–1.12 (m, 24H). 13 CNMR (100MHz, CDCl3) δ / ppm 145.66, 145.02, 137.87, 132.73, 126.21, 124.98, 30.04, 24.62, 23.53. HRESI-MS[M-Cl] + For [C] 29 H37 N4] + Calculated m / z value: 441.3013, measured value: 441.3013.

[0440] Flowchart 2 illustrates the synthesis of pyridine-fused NHC ligands.

[0441]

[0442] (c) Synthesis of 2-chloro-N-(2,4,6-triisopropylphenyl)pyridine-3-amine

[0443] A mixture of 2-chloropyridin-3-amine (1.28 g, 10 mmol), (diacetoxyiodine)benzene (15 mmol), and triisopropylbenzene (100 mmol) was stirred overnight in 40 mL of 1,1,1,3,3,3-hexafluoro-2-isopropanol at room temperature. After the reaction, the solvent was evaporated, and the residue was purified by column chromatography. Yield: 2.85 g, 86%. 1 H NMR(500MHz,CDCl3)δ / ppm 7.73(d,J=4.2Hz,1H),7.08(s,2H),6.95(dd,J=8.0,4.6Hz,1H),6.45(d,J=7.9Hz,1H),5.63(s,1H),3.02(dt ,J=13.7,6.9Hz,2H),2.93(dt,J=13.8,6.9Hz,1H),1.29(d,J=6.9Hz,6H),1.18(s,6H),1.10(d,J=6.8Hz,6H). 13 C NMR(101MHz,CDCl3)δ / ppm 148.90,147.37,141.30,137.21,136.38,130.83,123.54,122.29,119.07,77.55,77.23,76.91,34.48,28.66,24.79,24.29,23.39. HRESI-MS:[M+H] + For [C] 20 H 27 N2Cl] + Calculated m / z value: 331.1936, measured value: 331.1933.

[0444] (d)N 2 -(2,6-Diisopropylphenyl)-N 3 Synthesis of -(2,4,6-triisopropylphenyl)-pyridine-2,3-diamine

[0445] To P tPd2(dba)3 (100 mg, 0.11 mmol) was added to a 20 mL solution of Bu3 (100 mg, 0.50 mmol) in toluene. The dark red solution was stirred at room temperature for five minutes. Then 2,6-diisopropylaniline (355 mg, 2.0 eq.), 2-chloro-N-(2,4,6-triisopropylphenyl)pyridine-3-amine (330 mg, 1.0 eq.), and NaO were added. t Bu (289 mg, 3.0 eq.) was added to the solution through a single port. The resulting suspension was heated at 130 °C for two days. After the reaction, the solution was passed through a diatomaceous earth pad and evaporated to dryness. The residue was purified by silica gel column chromatography. Yield: 167 mg, 35%. 1 H NMR(500MHz,CDCl3)δ / ppm 7.69(d,J=4.2Hz,1H),7.36–7.31(m,1H),7.29(d,J=7.3Hz,2H),7.13(s,2H),6.58–6.49(m,2H),6.06(s,1H),4.82(s,1H),3 .25(dt,J=13.7,6.8Hz,2H), 3.13(dt,J=13.6,6.8Hz,2H), 2.98(dt,J=13.8,6.9Hz,1H), 1.26(d,J=5.7Hz,24H), 1.20(s,6H). 13 CNMR(101MHz,CDCl3)δ / ppm 149.50,146.83,145.88,144.72,139.01,135.13,133.35,131.35,127.06,123.63,121.94,121.11,114.82,34.22,28.77,28.36,24.20. HRESI-MS:[M+H] + For [C] 32 H 45 N3] + Calculated m / z value: 472.3686, measured value: 472.3680.

[0446] (e) Synthesis of 3-(2,6-diisopropylphenyl)-1-(2,4,6-triisopropylphenyl)-1H-imidazo[4,5-b]pyridine-3-onium tetrafluoroborate (PyIPr-BF4)

[0447] N 2 -(2,6-Diisopropylphenyl)-N 3A solution of triethyl orthoformate of (2,4,6-triisopropylphenyl)-pyridine-2,3-amine (500 mg, 1.06 mmol). The mixture was then heated at 150 °C for several hours. The mixture was then cooled to room temperature and excess trimethylchlorosilane was added. The resulting reaction mixture was heated at 70 °C overnight. After the reaction, the solvent was evaporated, a methanol solution of HBF4 was added, and the mixture was stirred at room temperature for 30 min. Subsequently, the solution was extracted with dichloromethane and a saturated aqueous solution of NaHCO3. The organic layer was dried over MgSO4 and evaporated to give a white solid of 3-(2,6-diisopropylphenyl)-1-(2,4,6-triisopropylphenyl)-1H-imidazo[4,5-b]pyridine-3-onium tetrafluoroborate. 1 H NMR(500MHz,CDCl3)δ / ppm 10.32(s,1H),8.85(d,J=4.4Hz,1H),7.90(d,J=8.3Hz,1H),7.76(dd,J=8.2,4.6Hz,1H),7.66(d,J=7.8Hz,2H),7.45(d,J=7.8Hz,3H),7.27(s ,2H),3.04(dt,J=13.6,6.8Hz,2H),2.22(td,J=13.4,6.6Hz,5H),1.35(d,J=6.8Hz,7H),1.28(dd,J=6.5,2.9Hz,15H),1.13(t,J=6.2Hz,15H). 19 F NMR (471MHz, CDCl3) δ / ppm-151.89,-151.94. 11 B NMR (160MHz, CDCl3) δ-1.31. 13 C NMR(126MHz,CDCl3)δ / ppm 153.89,151.06,146.34,145.86,145.57,144.31,132.77,126.57,126.18,125.08, 124.63,124.29,123.47,123.06,34.73,30.01,29.80,24.55,24.09,24.02,23.91. HRESI-MS:[M-BF4] + For [C] 33 H 44 N3] + Calculated m / z value: 482.3529, measured value: 482.3516.

[0448] (ii) Synthesis of metal carbene complexes

[0449] Flowchart 3 illustrates the synthesis of metal carbene complexes.

[0450]

[0451]

[0452] (a) Synthesis of the complex precursor PzImCuCl

[0453] To KO t PzIm-Cl (1.0 eq.) and CuCl (1.2 eq.) were added to a THF solution of Bu (1.2 eq.). The resulting mixture was stirred overnight at room temperature under argon atmosphere. After the reaction, the reaction mixture was passed through a layer of diatomaceous earth and then evaporated to dryness. The product was washed with EtOH and n-hexane. 1 ¹H NMR (500MHz, CDCl₃) δ / ppm 1 H NMR (500MHz, CDCl3) δ8.52 (s, 2H), 7.62 (t, J = 7.5Hz, 2H), 7.42 (d, J = 7.6Hz, 4H), 2.38–2.27 (m, 4H), 1.30 (d, J = 6.2Hz, 12H), 1.12 (d, J = 6.4Hz, 12H). 13 C NMR (126MHz, CDCl3) δ / ppm 193.51, 146.31, 141.20, 140.18, 131.81, 130.38, 124.93, 29.63, 24.94, 23.84.

[0454] (b) Synthesis of the complex precursor PzImAuCl

[0455] KO was added to the THF suspension of PzIm-Cl (1.0 eq.) t Bu (1.2 eq.) was added, and the resulting mixture was stirred at room temperature under argon for 1 hour, during which time the solution gradually became clear. Au(tht)Cl (1.2 eq.) was then added, and the reaction mixture was stirred in the dark for 16 hours. After the reaction, the mixture was filtered through a diatomaceous earth mat and then evaporated to dryness. The product was washed with EtOH and n-hexane. Yield: 185 mg, 27%. 1 H NMR(500MHz,CDCl3)δ / ppm 8.55 (s, 2H), 7.63 (t, J = 7.8Hz, 2H), 7.41 (d, J = 7.8Hz, 4H), 2.33 (dt, J = 13.8, 6.9Hz, 4H), 1.34 (d, J = 6.9Hz, 12H), 1.10 (t, J = 7.9Hz, 12H). 13C NMR (126MHz, CDCl3) δ / ppm 188.22, 146.16, 141.49, 139.91, 131.70, 129.88, 124.75, 29.50, 24.40, 23.82.

[0456] (c) Synthesis of the complex precursor PzImAgCl

[0457] Add Ag₂O (1.0 eq.) to a DCM solution of PzIm-Cl (1.0 eq.). Stir the resulting suspension overnight in the dark at room temperature. After the reaction, filter the reaction mixture through a diatomaceous earth mat and then evaporate to dryness. Wash the product with EtOH and n-hexane. 1 H NMR (500MHz, CDCl3) δ / ppm8.56 (s, 1H), 7.63 (t, J = 7.7Hz, 1H), 7.42 (d, J = 7.8Hz, 2H), 2.31(dt,J=13.5,6.8Hz,3H), 1.28(d,J=6.8Hz,7H), 1.11(d,J=6.7Hz,8H). 13 C NMR (126MHz, CDCl3) δ / ppm 146.32, 141.47, 140.12, 131.97, 130.65, 125.06, 29.60, 24.86, 23.96.

[0458] (d) General procedure for complex synthesis

[0459] Add NaO to a THF solution of a carbazole derivative (1.5 eq.) or a THF solution of a pyrido[3,4-b]indole derivative (1.5 eq.). t Bu (1.5 eq.) was added, and the mixture was stirred at room temperature under argon for 30 min. Then NHC-M-Cl (1.0 eq.) was added, and the reaction mixture was stirred overnight in the dark. After the reaction, the mixture was passed through a diatomaceous earth mat. The filtrate was evaporated to dryness, and the product was washed with n-hexane.

[0460] Cu1: 1 H NMR(500MHz,CD2Cl2)δ / ppm 8.59(s,2H),7.85(d,J=7.6Hz,4H),7.59(d,J=7.8Hz,2H),6.96(t,J=7.5Hz,2H),6.85(t,J=7.3H z, 2H), 6.23 (d, J = 8.1Hz, 2H), 2.54–2.45 (m, 4H), 1.26 (d, J = 6.8Hz, 12H), 1.18 (d, J = 6.8Hz, 12H). 13C NMR(126MHz,CD2Cl2)δ / ppm 194.61,149.71,146.96,141.06,140.27,131.49,130.91,124.84,123.88,123.40,119.10,115.44,114.06,29.52,24.42,23.50。

[0461] Cu2: 1 H NMR(500MHz,CD2Cl2)δ / ppm 8.59(s,2H),8.16(s,1H),7.90–7.79(m,3H),7.58(d,J=7.3Hz,4H),7.17(d,J=8.1Hz,1H),7.05(t,J=7.5Hz,1H),6.95(t,J=6.9Hz,1H),6.27(d,J=7.8Hz,1H),6.12(d,J=8.5Hz,1H),2.46(m,4H),1.22(d,J=6.3Hz,12H),1.16(d,J=6.1Hz,12H)。 13 C NMR(151MHz,CD2Cl2)δ / ppm 194.40,152.20,150.93,147.54,141.87,140.72,132.15,131.40,127.06,125.54,125.46,124.98,124.60,123.85,122.50,120.14,117.89,115.16,114.93,97.47,30.08,25.02,24.04。

[0462] Cu3: 1 H NMR(500MHz,CD2Cl2)δ / ppm 8.58(s,2H),7.87–7.80(m,4H),7.60(d,J=7.8Hz,4H),7.02(d,J=8.5Hz,2H),6.17(d,J=8.5Hz,2H),2.50(dt,J=13.5,6.7Hz,4H),1.37(s,18H),1.28(d,J=6.8Hz,12H),1.18(d,J=6.7Hz,12H)。 13 C NMR(126MHz,CD2Cl2)δ / ppm 195.21,148.72,147.33,141.40,140.69,138.38,131.88,131.31,125.22,124.08,121.55,115.42,113.75,34.70,32.36,29.93,24.89,23.90。

[0463] Cu4: 1 H NMR(500MHz,CD2Cl2)δ / ppm 8.61(s,2H),8.18(s,2H),7.87(t,J=7.9Hz,2H),7.68(d,J=7.6Hz,4H),7.62(d,J=7.9Hz,4H),7.42(t,J=7.5Hz,4H),7.30(d,J=8.3 Hz, 2H), 7.25 (t, J = 7.3Hz, 2H), 6.30 (d, J = 8.4Hz, 2H), 2.52 (dq, J = 13.8, 6.9Hz, 4H), 1.30 (d, J = 6.8Hz, 12H), 1.20 (d, J = 6.7Hz, 12H). 13 C NMR(126MHz,CD2Cl2)δ / ppm 194.85,150.39,147.42,143.41,141.56,140.68,131.98,131.34,129.28,128.9 6,127.16,125.89,125.31,125.10,123.66,118.10,114.85,29.97,24.90,23.93. MALDI-TOF:[C 53 H 52 CuN5]m / z, calculated m / z value: 821.35, measured: 821.28. C 53 H 52 Analytical values ​​of CuN5+H2O: C, 75.73; H, 6.48; N, 8.33; Measured values: C, 75.71; H, 6.26; N, 8.10.

[0464] Cu5: 1 H NMR(500MHz,CD2Cl2)δ / ppm 8.64(s,2H),8.03(d,J=3.9Hz,1H),7.96(d,J=7.8Hz,1H),7.89(t,J=7.9Hz,2H),7.77(d,J=4.9Hz,1H),7.70(s,1H),7.63(d,J=7.9Hz,4H),7. 12(t,J=7.4Hz,1H), 6.96(t,J=7.3Hz,1H), 6.30(d,J=8.2Hz,1H), 2.52(dt,J=13.7,6.8Hz,4H), 1.29(d,J=6.8Hz,12H), 1.21(d,J=6.8Hz,12H).

[0465] Au1: 1H NMR(400MHz,CD2Cl2)δ / ppm 8.58(s,2H),7.87(d,J=7.6Hz,2H),7.79(t,J=7.9Hz,2H),7.54(d,J=7.9Hz,4H),7.08–6.99(m,2H),6.91–6.82(m,2H),6.61(d,J=8.1Hz,2H),2.48(dt,J=13.7,6.9Hz,4H),1.32(d,J=6.9Hz,12H),1.14(d,J=6.9Hz,12H)。 13 C NMR(126MHz,CD2Cl2)δ / ppm149.77,147.49,141.94,140.93,132.07,131.13,125.29,124.25,124.14,119.73,116.70,113.92,30.15,24.59,24.31。

[0466] Au2: 1 H NMR(500MHz,CD2Cl2)δ / ppm 8.61(s,1H),8.20(s,0H),7.91(d,J=7.7Hz,1H),7.80(t,J=7.8Hz,1H),7.55(d,J=7.8Hz,2H),7.26(d,J=8.4Hz,0H),7.13(t,J=7.6Hz,1H),6.99(t,J=7.4Hz,1H),6.66(d,J=8.2Hz,0H),6.56(d,J=8.4Hz,1H),2.46(dt,J=13.6,6.8Hz,2H),1.31(d,J=6.8Hz,6H),1.15(d,J=6.8Hz,6H)。 13 C NMR(126MHz,CD2Cl2)δ / ppm 190.53,151.14,149.91,146.94,141.65,140.23,131.61,130.47,126.65,125.11,124.78,124.51,123.87,123.08,121.68,119.63,117.88,113.96,113.77,97.74,29.59,24.04,23.74。

[0467] Au3: 1H NMR(500MHz,CD2Cl2)δ / ppm 8.62(s,2H),8.19(dd,J=10.7,5.9Hz,2H),7.92(d,J=7.8Hz,1H),7.77(t,J=7.8Hz,2H),7.55(d,J=7.8Hz,4H),7.16–7.09(m,1H),6.98( t,J=7.4Hz,1H),6.90–6.83(m,1H),6.72(d,J=8.1Hz,1H),2.55(dt,J=13.1,6.6Hz,4H),1.44(d,J=6.8Hz,12H),1.18(d,J=6.8Hz,12H). 13 C NMR(126MHz,CD2Cl2)δ / ppm 191.17,148.59,146.78,145.01,141.46,140.29,131.44,130.46,126.52,124.6 9,124.43,121.92,119.80,116.83,116.13,113.65,112.28,29.59,23.98,23.67.

[0468] Ag1: 1 H NMR(500MHz,CD2Cl2)δ / ppm 8.61(s,2H),7.87(d,J=7.5Hz,2H),7.75(t,J=7.7Hz,2H),7.53(d,J=7.7Hz,4H),7.02(t,J=7.4Hz,2H),6.84(t,J =7.2Hz, 2H), 6.57 (d, J = 8.0Hz, 2H), 2.46 (dt, J = 13.1, 6.5Hz, 4H), 1.30 (d, J = 6.6Hz, 12H), 1.15 (d, J = 6.6Hz, 12H). 13 C NMR (126MHz, CD₂Cl₂) δ / ppm: 150.27, 146.80, 141.55, 140.18, 131.69, 131.15, 124.93, 123.82, 123.41, 119.25, 115.08, 114.10, 29.57, 24.48, 23.71. Note: No carbonium carbon was observed. 13 C signal.

[0469] Flowchart 4 illustrates the synthesis of metal carbene complexes.

[0470]

[0471] (e) General procedure for synthesizing the complex precursor PyIPr-M-Cl

[0472] KHMDS (1.5 eq.) was added to a suspension of PyIPr-BF4 (1.0 eq.), followed by CuCl or Au(tht)Cl (1.5 eq.). The resulting mixture was stirred overnight at room temperature under argon atmosphere. After the reaction, the suspension was passed through a diatomaceous earth layer and evaporated to dryness. The product was purified by recrystallization in DCM / EtOH.

[0473] PyIPrCuCl: 1 H NMR(500MHz,CDCl3)δ / ppm 8.52(dd,J=4.7,1.3Hz,1H),7.58(t,J=7.8Hz,1H),7.49(dd,J=8.1,1.3Hz,1H),7.40(d,J=7.8Hz,2H),7.35(dd,J=8.2,4.7Hz,1H),7.21(s, 2H), 3.03 (dt, J=13.8, 6.9Hz, 1H), 2.36 (tt, J=13.6, 6.8Hz, 4H), 1.36 (d, J=6.9Hz, 6H), 1.29 (d, J=6.8Hz, 12H), 1.11 (dd, J=6.7, 5.7Hz, 12H). 13 C NMR(101MHz,CDCl3)δ / ppm 190.09,151.93,147.00,146.75,146.39,146.08,131.39,130.95,129.02,127.64,124 .73,122.94,120.29,120.18,34.65,29.46,29.25,25.28,24.95,24.14,24.01,23.76. HRESI-MS: [M-Cl+MeCN] + For [C] 35 H 46 N4Cu] + Calculated m / z value: 585.3013, measured value: 585.3026.

[0474] PyIPrAuCl: 1H NMR(500MHz,CDCl3)δ / ppm 8.54–8.51(m,1H),7.59(t,J=7.8Hz,1H),7.51–7.48(m,1H),7.42–7.35(m,4H),7.22–7.18(m,3H),3.02(dt, J=13.8,6.9Hz,1H),2.40–2.28(m,6H),1.37(d,J=6.9Hz,8H),1.33(d,J=6.9Hz,16H),1.09(t,J=6.4Hz,17H). 13 C NMR(101MHz,CDCl3)δ / ppm 184.52,151.83,146.90,146.44,146.22,145.89,131.29,130.48,128.43,127.37,124 .55,122.80,120.58,120.20,34.43,29.32,29.11,24.73,24.41,24.01,23.92,23.71. HRESI-MS: [M-Cl+MeCN] + For [C] 35 H 46 N4Au] + Calculated m / z value: 719.3388, measured value: 719.3378.

[0475] (f) General procedure for complex synthesis

[0476] Add NaO to a THF solution of a carbazole derivative (1.5 eq.) or a THF solution of a pyrido[3,4-b]indole derivative (1.5 eq.). t Bu (1.5 eq.) was added, and the mixture was stirred at room temperature under argon for 30 min. Then PyIPr-M-Cl (1.0 eq.) was added, and the reaction mixture was stirred overnight in the dark. After the reaction, the mixture was passed through a diatomaceous earth mat. The filtrate was evaporated to dryness, and the product was washed with n-hexane.

[0477] Cu6: 11H NMR (500 MHz, acetone-d6) δ / ppm 8.63 (dd, J = 4.7, 1.2 Hz, 1H), 7.98 (dd, J = 8.1, 1.2 Hz, 1H), 7.86 (t, J = 7.8 Hz, 1H), 7.81 (d, J = 7.6 Hz, 2H), 7.69–7.62 (m, 3H), 7.58 (s, 2H), 6.92–6.87 (m, 2H), 6.77 (t, J = 7.1 Hz, 2H), 6.32 (d, J = 8.1 Hz, 2H), 3.25 (dt, J = 13.8, 6.9 Hz, 1H), 2.63 (ddt, J = 13.7, 10.6, 6.8 Hz, 4H), 1.50 (d, J = 6.9 Hz, 6H), 1.28 (dd, J = 14.1, 6.9 Hz, 12H), 1.22 (d, J = 6.9 Hz, 6H), 1.18 (d, J = 6.9 Hz, 6H). 13 13C NMR (126 MHz, acetone-d6) δ / ppm 191.90, 153.21, 150.92, 148.10, 148.06, 147.77, 147.63, 132.81, 131.89, 130.58, 128.62, 125.50, 125.12, 124.18, 123.77, 121.83, 121.55, 119.83, 116.16, 115.05, 35.49, 25.34, 24.98, 24.59, 24.11, 23.98.

[0478] Cu7: 1 1H NMR (500 MHz, acetone-d6) δ / ppm = 8.73 (s, 2H), 8.22 (s, 1H), 7.99–7.93 (m, 2H), 7.87 (d, J = 7.6 Hz, 1H), 7.74 (d, J = 7.8 Hz, 4H), 7.70 (d, J = 7.6 Hz, 1H), 7.40 (d, J = 7.4 Hz, 1H), 7.26–7.20 (m, 1H), 7.16–7.10 (m, 1H), 6.90–6.85 (m, 1H), 6.83–6.77 (m, 1H), 6.54 (s, 1H), 6.13 (d, J = 7.7 Hz, 1H), 2.73 (dd, J = 14.0, 7.3 Hz, 4H), 1.43 (s, 6H), 1.32 (d, J = 6.8 Hz, 12H), 1.20 (d, J = 6.7 Hz, 12H).

[0479] Cu8: 11H NMR (500 MHz, acetone-d6) δ / ppm 8.63 (d, J = 4.6 Hz, 1H), 8.23 (s, 1H), 7.94 (t, J = 7.6 Hz, 2H), 7.88 (d, J = 7.6 Hz, 1H), 7.71 (dd, J = 12.6, 7.7 Hz, 3H), 7.65 (dd, J = 8.0, 4.4 Hz, 1H), 7.60 (s, 2H), 7.40 (d, J = 7.3 Hz, 1H), 7.22 (t, J = 7.3 Hz, 1H), 7.12 (t, J = 7.3 Hz, 1H), 6.89 (t, J = 7.4 Hz, 1H), 6.79 (t, J = 7.3 Hz, 1H), 6.60 (s, 1H), 6.24 (d, J = 8.0 Hz, 1H), 3.27 (dt, J = 13.7, 6.8 Hz, 1H), 2.72–2.61 (m, 4H), 1.51 (d, J = 6.9 Hz, 6H), 1.41 (s, 6H), 1.32 (d, J = 6.8 Hz, 12H), 1.21 (dd, J = 14.6, 6.8 Hz, 12H).

[0480] Au4: 1 1H NMR (500 MHz, CD2Cl2) δ / ppm 8.57 (dd, J = 4.7, 1.1 Hz, 1H), 7.89 (d, J = 7.6 Hz, 2H), 7.78 (t, J = 7.8 Hz, 1H), 7.66 (dd, J = 8.1, 1.1 Hz, 1H), 7.54 (d, J = 7.9 Hz, 2H), 7.48 (dd, J = 8.1, 4.7 Hz, 1H), 7.39 (s, 2H), 7.03 (t, J = 7.6 Hz, 2H), 6.87 (t, J = 7.3 Hz, 2H), 6.67 (d, J = 8.1 Hz, 2H), 3.15 (dt, J = 13.8, 6.9 Hz, 1H), 2.59–2.45 (m, 4H), 1.46 (d, J = 6.9 Hz, 6H), 1.34 (t, J = 6.6 Hz, 12H), 1.16 (t, J = 7.0 Hz, 12H). 13 13C NMR (126 MHz, CD2Cl2) δ / ppm 188.61, 152.72, 149.71, 147.44, 147.34, 147.05, 147.02, 131.61, 131.43, 129.34, 128.10, 124.88, 124.01, 123.91, 123.13, 121.08, 120.45, 119.52, 116.29, 113.80, 35.14, 29.82, 29.66, 24.72, 24.45, 24.35, 24.31, 24.05.

[0481] Au5: 1 H NMR(500MHz,High-d6)δ / ppm 8.77(s,2H),8.16(s,1H),8.04(d,J5.1Hz,1H),8.00(d,J7.8Hz,1H) ,7.87(t,J7.9Hz,2H),7.81(d,J5.0Hz,1H),7.68(d,J7.9Hz,4H),7 16(t,J7.6Hz,1H),6.94(t,J7.2Hz,1H),6.75(d,J8.3Hz,1H),2.70( dt,JH13.7,6.8Hz,4H),1.39(d,J6.9Hz,12H),1.18(d,J6.8Hz,12H). 13 C NMR(126MHz,High-d6)δ / ppm 190.94,151.06,148.05,146.42,142.95,141.50,137.61,136.85,132.54,131.88 ,129.14,126.83,125.70,123.10,121.65,117.91,115.57,114.42,24.73,24.32.

[0482] Au6: 1 H NMR(500MHz,High-d6)δ / ppm 8.80(s,2H),8.51(s,2H),7.93(t,J7.8Hz,2H),7.71(d,J7.9Hz,4H),7.44(d,J8.5Hz,2H),6 73(d,J6.5Hz,2H),2.69(dt,J13.7,6.9Hz,4H),1.36(d,J6.8Hz,12H),1.18(d,J6.8Hz,12H). 13 C NMR(126MHz,CD2Cl2)δ / ppm 189.43,151.88,146.95,141.89,140.12,131.70,130.40,128.06,124.97,124.83,123.23,120.89,114.51,99.90,29.60,24.06,23.73.

[0483] Au7: 1H NMR(500MHz,High-d6)δ / ppm 8.75(s,2H),8.28(s,1H),7.95–7.80(m,3H),7.85–7.69(m,5H),7 (d,J7.5Hz,1H),7.24(t,J7.5Hz,1H),7.14(t,J7.5Hz,1H),6.98(t ,JC8.0Hz,1H),6.85(t,J7.0Hz,1H),6.65(d,J8.0Hz,1H),2.74–2.6 5(m,4H),1.44(s,6H),1.40(d,J7.0Hz,12H),1.18(d,J7.0Hz,12H).

[0484] Au8: 1 H NMR(500MHz,High-d6)δ / ppm 8.65(dd,J4.7,1.2Hz,1H),8.00(dd,J8.1,1.2Hz,1H),7.93(d,J1.8Hz,2H),7.82(t,J7.8H). z,1H),7.68(dd,J8.1,4.8Hz,1H),7.63(d,J7.9Hz,2H),7.56(s,2H),7.08(dd,J8.5,2.0Hz,2 H),6.66(d,JS8.5Hz,2H),3.24(dt,JS13.8,6.9Hz,1H),2.63(tt,J13.7,6.9Hz,4H),1.50(d,J M6.9Hz,6H),1.38(t,J6.9Hz,12H),1.35(s,18H),1.21(d,J6.9Hz,6H),1.17(d,J6.9Hz,6H). 13 CNMR(126MHz,High-d6)δ / ppm 189.11,153.17,148.99,147.94,147.77,139.02,132.48,131.90,130.26,128.71,125.33,124.77,123 .72,122.18,122.01,121.60,115.81,113.74,35.52,35.00,32.67,24.93,24.66,24.52,24.42,24.19.

[0485] Au9: 1H NMR(500MHz,acetone-d6)δ / ppm 8.66(dd,J=4.7,1.1Hz,1H),8.02(dd,J=8.1,1.1Hz,1H),7.91–7.81(m,2H),7.70(dd,J=8.2,4.7Hz,1 H),7.64(d,J=7.9Hz,2H),7.61–7.53(m,3H),7.02(t,J=7.2Hz,1H),6.83(t,J=7.3Hz,1H),6.81–6.76 (m,1H),6.73(d,J=8.2Hz,1H),6.61(dd,J=8.8,4.6Hz,1H),3.23(dq,J=14.0,7.0Hz,1H),2.62(tt,J= 13.6, 6.8Hz, 4H), 1.49 (d, J = 6.9Hz, 6H), 1.36 (dd, J = 11.9, 6.9Hz, 12H), 1.19 (dd, J = 20.0, 6.9Hz, 12H). 19 F NMR (471MHz, acetone-d6) δ / ppm -129.97. 13 C NMR (126MHz, acetone-d6) δ / ppm 188.42,157.63,155.81,153.29,151.43,148.02,147.92,147.87,147.80,146.74,132.47,131.96,130.17,128.69,125.39,124.98,124.80,124.72,124. 65,124.61,123.70,122.30,121.74,120.43,116.86,114.58,114.52,114.45,111.85,111.65,105.07,104.88,35.48,24.91,24.58,24.54,24.40,24.22.

[0486] Flowchart 5 illustrates the synthesis of metal carbene complexes (Cu9, Cu10, and Cu11 with π-extended pyrazine-fused NHC ligands).

[0487]

[0488] Cu9: 1H NMR(500MHz,acetone-d6)δ / ppm 8.23(dd,J=6.5,3.5Hz,2H),8.00–7.96(m,2H),7.95(t,J=7.9Hz,2H),7.82(d,J=7.6Hz,2H),7.74(d,J=7.9Hz,4H),6.96–6.90 (m,2H),6.83–6.77(m,2H),6.28(d,J=8.1Hz,2H),2.86(dt,J=13.7,6.8Hz,4H),1.30(d,J=6.9Hz,12H),1.19(d,J=6.8Hz,12H).

[0489] Cu10: 1 ¹H NMR (500MHz, CD₂Cl₂) δ / ppm 8.27(dd,J=6.5,3.5Hz,2H),7.95–7.86(m,4H),7.80(d,J=7.6Hz,1H),7.64(d, J=7.9Hz, 4H), 7.50 (dd, J=9.5, 2.5Hz, 1H), 6.99 (t, J=7.1Hz, 1H), 6.85 (t, J=7. 3Hz,1H),6.77–6.71(m,1H),6.23(d,J=8.1Hz,1H),6.09(dd,J=8.8,4.5Hz,1H) ,2.60(dt,J=13.6,6.7Hz,4H), 1.27(d,J=6.9Hz,12H), 1.19(d,J=6.8Hz,12H).

[0490] Cu11: 1 H NMR(500MHz,CD2Cl2)δ / ppm 8.26(dd,J=6.4,3.5Hz,2H),7.93–7.85(m,4H),7.68–7.59(m,4H),6.79(d,J=7.6Hz,2H),6.09 (d, J = 8.2 Hz, 2H), 2.60 (dt, J = 13.6, 6.8 Hz, 4H), 1.27 (d, J = 6.8 Hz, 12H), 1.19 (d, J = 6.8 Hz, 12H).

[0491] Flowchart 6 illustrates the synthesis of metal carbene complexes (Au10 and Au11 with π-extended pyrazine-fused NHC ligands).

[0492]

[0493] Au10: 1H NMR(500MHz,CD2Cl2)δ / ppm 8.26(dd,J=6.4,3.5Hz,1H),7.89(ddd,J=20.1,11.2,5.6Hz,3H),7.62(d,J=7.9Hz,2H),7.06(t,J=7.4Hz,1H),6.90 (t,J=7.3Hz,1H),6.61(d,J=8.1Hz,1H),2.60(dt,J=13.6,6.8Hz,2H),1.36(d,J=6.8Hz,7H),1.18(d,J=6.8Hz,7H). 13 C NMR(126MHz,CD2Cl2)δ / ppm 198.43,149.76,147.78,141.36,140.88,132.14,131.37,130.90,129.7 6,125.44,124.37,124.20,119.75,116.87,113.97,30.25,24.61,24.42.

[0494] Au11: 1 H NMR(400MHz,CD2Cl2)δ / ppm 8.26(dd,J=6.5,3.5Hz,2H),7.94–7.83(m,6H),7.62(d,J=7.9Hz,4H),7.12(dd,J=8.5,1.8Hz,2H),6.53(d ,J=8.5Hz,2H),2.60(dt,J=13.7,6.8Hz,4H),1.38(s,18H),1.37(d,J=7.0Hz,12H),1.18(d,J=6.8Hz,12H). 13 CNMR(101MHz,CD2Cl2)δ / ppm 198.71,148.28,147.74,141.33,140.94,139.53,132.12,131.38,130.82,129. 73,125.41,124.16,121.96,115.67,113.26,34.91,32.50,30.24,24.66,24.42.

[0495] The structures of Cu7-Cu11 and Au5-Au11 are shown below:

[0496]

[0497]

[0498] result

[0499] The results of this work are shown below.

[0500] The photophysical properties of complexes can be determined by the maximum emission wavelength (λ). em ), launch lifetime (τ) em ), emission quantum yield (Ф) em ), radiation attenuation rate (k r ), and non-radiative attenuation rate (k nr Evaluation. The complex in degassed toluene and MCP (1,3-bis(N-carbazolyl)benzene) films. em The values ​​were obtained directly by absolute measurement using a Hamamatsu C11347 Quantaurus-QY Absolute PL quantum yield spectrometer (PL stands for photoluminescence). The maximum emission wavelength λ was read from the emission spectrum. em The emission lifetime (τ) was measured on a Quanta Ray GCR150-10 pulsed Nd:YAG laser system (pulse output: 355 nm). em Measurement. Monitor the intensity of emission attenuation as a function of time.

[0501] I(t) = J0e -t / τ

[0502] I0 is the initial emission intensity, I(t) is the emission intensity at time t, τ is the emission lifetime, and t is time.

[0503] The emission lifetime was determined by fitting exponential decay using Origin software. The k-value of the complex... r and k nr Equation k can be used separately r =Ф em / τ em and k nr =(1-Ф em ) / τ em calculate.

[0504] Photophysical characterization of compounds

[0505] Table 1. Summary of photophysical properties measured in different media

[0506]

[0507] a Weighted average life

[0508] Table 1 (continued). Summary of photophysical properties measured in different media

[0509]

[0510]

[0511] a Weighted average life

[0512] Table 2. Device data for Cu1

[0513]

[0514] Table 3. Device lifetime measurement of Cu1. Device structure: ITO / HAT-CN (5nm) / PT-301 (160nm) / PT-603I (5nm) / Cu1:LLP604 (20nm) / PT74M (5nm) / LET321:Liq (1:1, 25nm) / Liq (1nm) / Al (100nm)

[0515]

[0516]

[0517] n represents LT(L1) = LT(L0) × (L0 / L1) n acceleration coefficient

[0518] Table 4. Device data for Cu2

[0519]

[0520] Table 5a. Device lifetime measurement of Cu2. Device structure: ITO / HAT-CN (5nm) / PT-301 (160nm) / PT-603I (5nm) / Cu2:LLP604 (20nm) / PT74M (5nm) / LET321:Liq (1:1, 25nm) / Liq (1nm) / Al (100nm)

[0521]

[0522] n represents LT(L1) = LT(L0) × (L0 / L1) n acceleration coefficient

[0523] Table 5b. Device data for Cu2 (device structure is the same as in Table 5a)

[0524]

[0525] Table 6. Device data for Cu3

[0526]

[0527]

[0528] Table 7. Device lifetime measurement of Cu3. Device structure: ITO / HAT-CN (5nm) / PT-301 (160nm) / PT-603I (5nm) / Cu3:LLP604 (20nm) / PT74M (5nm) / LET321:Liq (1:1, 25nm) / Liq (1nm) / Al (100nm).

[0529]

[0530] n represents LT(L1) = LT(L0) × (L0 / L1) n acceleration coefficient

[0531] Table 8. Device data for Au1

[0532]

[0533] Table 9. Device lifetime measurement of Au1. Device structure: ITO / HAT-CN (5nm) / PT-301 (160nm) / PT-603I (5nm) / Au1:LLP604 (30nm) / PT74M (5nm) / LET321:Liq (1:1, 25nm) / Liq (1nm) / Al (100nm)

[0534]

[0535] n represents LT(L1) = LT(L0) × (L0 / L1) n acceleration coefficient

[0536] Table 9a. Device lifetime measurement of Au1. Device structure: ITO / HAT-CN (10nm) / FSFA (60nm) / NPB-BC (5nm) / Au1:NPB-BC:A1 (30nm) / ANT-Biz (5nm) / ANT-Biz:Liq (1:1, 25nm) / Liq (2nm) / Al (100nm).

[0537]

[0538] n represents LT(L1) = LT(L0) × (L0 / L1) n acceleration coefficient

[0539] Table 10. Device data for Au2 in device structure (I)

[0540]

[0541] Table 11. Device data for Au2 in device structure (II)

[0542]

[0543] Table 12. Comparison with other Au(I) emitters

[0544]

[0545]

[0546] Table 13. Comparison with other Cu(I) emitters

[0547]

[0548] Table 14. Device data for Cu3 in device structure (II): ITO / HAT-CN (5nm) / PT-301 (160nm) / EB (5nm) / Cu3:RH (40nm) / HB (5nm) / ZADN:Liq (35:65,35nm) / Liq (1nm) / Al (100nm). (See also...) Figures 14A-14D )

[0549]

[0550]

[0551] Table 15. Device lifetime measurement of Cu3. Device structure (II): ITO / HAT-CN (5nm) / PT-301 (160nm) / EB (5nm) / Cu3:RH (40nm) / HB (5nm) / ZADN:Liq (35:65,35nm) / Liq (1nm) / Al (100nm)

[0552]

[0553] n represents LT(L1) = LT(L0) × (L0 / L1) n acceleration coefficient

[0554] Table 16. Device data for Cu4 in device structure (I): ITO / HAT-CN (5nm) / TAPC (40nm) / TCTA (10nm) / TCTA:TPBi:Cu4 (20nm) / TPBi (50nm) / LiF (1nm) / Al (100nm). (See also...) Figures 15A-15D )

[0555]

[0556] Table 17. Device data for Cu4 in device structure (II): ITO / HAT-CN (5nm) / PT-301 (160nm) / PT-603I (5nm) / Cu4:LLP604 (20nm) / PT74M (5nm) / LET321:Liq (1:1, 25nm) / Liq (1nm) / Al (100nm). (See also...) Figures 16A-16D )

[0557]

[0558] Table 18. Device lifetime measurement of Cu4. Device structure (II): ITO / HAT-CN (5nm) / PT-301 (160nm) / PT-603I (5nm) / Cu4:LLP604 (20nm) / PT74M (5nm) / LET321:Liq (1:1, 25nm) / Liq (1nm) / Al (100nm).

[0559]

[0560]

[0561] n represents LT(L1) = LT(L0) × (L0 / L1) n acceleration coefficient

[0562] Table 19. Device data for Au2 in device structure (III): ITO / HAT-CN (5nm) / PT-301 (160nm) / PT-603I (5nm) / Au2:LLP604 (20nm) / PT74M (5nm) / LET321:Liq (1:1, 25nm) / Liq (1nm) / Al (100nm). (See also...) Figures 17A-17D )

[0563]

[0564] Table 20. Device lifetime measurement of Au2. Device structure (III): ITO / HAT-CN (5nm) / PT-301 (160nm) / PT-603I (5nm) / Au2:LLP604 (20nm) / PT74M (5nm) / LET321:Liq (1:1, 25nm) / Liq (1nm) / Al (100nm).

[0565]

[0566] n represents LT(L1) = LT(L0) × (L0 / L1) n acceleration coefficient

[0567] Table 21. Device lifetime measurement of Au complexes with 3,5-dimethylphenyl groups a Device structure: ITO / HAT-CN (5nm) / PT-301 (160nm) / Spiral-3-BFP (15nm) / Au complex: DMIC-TRz: DMIC-Cz (15nm) / LET003 (20nm) / Liq (1nm) / Al (100nm)

[0568]

[0569] n represents LT(L1) = LT(L0) × (L0 / L1) n acceleration coefficient

[0570] a

[0571]

[0572] Table 22. Device data for Cu6 in TCTA:DPEPO co-body. Device structure: ITO / HAT-CN (5nm) / TAPC (40nm) / TCTA (10nm) / TCTA:DPEPO:Cu6 (20nm) / DPEPO (10nm) / TPBi (40nm) / LiF (1.2nm) / Al (100nm).

[0573]

[0574] Table 23. Device lifetime measurement of Cu6. Device structure: ITO / HAT-CN (10nm) / BPBPA (120nm) / mCBP (10nm) / mCBP:SiCzTrz:Cu6 (30nm) / SF3-TRz (5nm) / SF3-TRz:Liq (1:1, 25nm) / Liq (2nm) / Al (100nm).

[0575]

[0576] n represents LT(L1) = LT(L0) × (L0 / L1) n acceleration coefficient

[0577] Table 24. Device data for high-fluorescence OLEDs based on Cu6 and ν-DABNA (in mCBP). Device structure: ITO / HAT-CN (10nm) / BPBPA (120nm) / mCBP (10nm) / mCBP:Cu6:ν-DABNA (20nm) / SF3-TRz (5nm) / SF3-TRz:Liq (1:1, 25nm) / Liq (2nm) / Al (100nm).

[0578]

[0579]

[0580] Table 25. Device lifetime measurements of high-fluorescence OLEDs based on Cu6 and ν-DABNA (in mCBP). Device structure: ITO / HAT-CN (10nm) / BPBPA (120nm) / mCBP (10nm) / mCBP:Cu6:ν-DABNA (20nm) / SF3-TRz (5nm) / SF3-TRz:Liq (1:1, 25nm) / Liq (2nm) / Al (100nm).

[0581]

[0582] n represents LT(L1) = LT(L0) × (L0 / L1) n acceleration coefficient

[0583] Table 26. Device data for Cu7 in the DMIC-Cz:DMIC-Trz co-body. Device structure: ITO / HAT-CN (10nm) / BPBOA (80nm) / FSF4A (5nm) / DMIC-Cz:DMIC-Trz:Cu7 (30nm) / ANT-Biz (5nm) / ANT-Biz:Liq (25nm) / Liq (2nm) / Al (100nm).

[0584]

[0585] Table 27. Device data for high-fluorescence OLEDs based on Cu7 and MR-R (in RH). Device structure: ITO / HAT-CN (10nm) / HT (40nm) / EB (5nm) / Cu7:MR-R:RH (40nm) / HB (5nm) / ZADN:Liq (35:65) (35nm) / Liq (2nm) / Al (100nm)

[0586]

[0587] Table 28. Lifetime measurements of OLED devices based on Cu7 and MR-R (in RH). Device structure: ITO / HAT-CN (10nm) / HT (40nm) / EB (5nm) / Cu7:MR-R:RH (40nm) / HB (5nm) / ZADN:Liq (35:65) (35nm) / Liq (2nm) / Al (100nm).

[0588]

[0589]

[0590] n represents LT(L1) = LT(L0) × (L0 / L1) n acceleration coefficient

[0591] Table 29. Device data for high-fluorescence OLEDs based on Au3 and BN-2 (in mCBP). Device structure: ITO / HAT-CN (5nm) / TAPC (40nm) / mCBP (10nm) / Au3:BN-2:mCBP (20nm) / PPF (10nm) / TmPyPb (40nm) / LiF (1.2nm) / Al (100nm).

[0592]

[0593] Table 30. Device data for OLEDs based on Au5 in the mCBP:CzSiTrz co-substrate. Device structure: ITO / HAT-CN (10nm) / FSFA (120nm) / mCBP (10nm) / mCBP:CzSiTrz:Au5 (30nm) / SF3-Trz (5nm) / SF3-Trz:Liq (25nm) / Liq (2nm) / Al (100nm).

[0594]

[0595] Table 31. Device lifetime measurement of Au5. Device structure: ITO / HAT-CN (10nm) / FSFA (120nm) / mCBP (10nm) / mCBP:CzSiTrz:Au5 (30nm) / SF3-Trz (5nm) / SF3-Trz:Liq (25nm) / Liq (2nm) / Al (100nm).

[0596]

[0597] n represents LT(L1) = LT(L0) × (L0 / L1) n acceleration coefficient

[0598] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the disclosed invention pertains. Publications cited herein and the material they reference are specifically incorporated herein by reference. Furthermore, unless otherwise stated, the expression “wt%” means “wt / wt%”.

[0599] Those skilled in the art will recognize, or can determine, by conventional experimentation alone, numerous equivalents of the specific embodiments of the invention described herein. These equivalents are intended to be covered by the appended claims.

Claims

1. A compound having the following structure: Formula I in: The compounds are generally neutral, negatively charged, or positively charged. M is copper, and its oxidation state is 0, +1, +2, or +3. P' is selected from: , or , in: Ra can be hydrogen or isopropyl independently, and Rb is isopropyl. Z has the following structure: in: X1, X2, X3, X4, X5, and X6 are carbon, while X7 and X8 are either carbon or nitrogen. Rx1, Rx2, Rx4, and Rx5 are hydrogen, and Rx3, Rx6, Rx7, and Rx8 are independently hydrogen, halogen, cyano, unsubstituted C1-C18 alkyl, or unsubstituted C5-C26 aryl, wherein when the corresponding X7 or X8 is nitrogen, each Rx7 or Rx8 is absent, or the adjacent Rxn groups, together with the atoms in the ring to which they are bonded, independently form a five- or six-membered C1-C14 alkyl-substituted aryl group, wherein n in the adjacent Rxn groups is a consecutive integer pair of 1 to 4 or 5 to 8.

2. The compound of claim 1, wherein Rx3, Rx6, Rx7 and Rx8 are independently hydrogen, halogen, methyl, cyano, tert-butyl or phenyl.

3. The compound of claim 1, having the following structure: Style VI in: W represents carbon or nitrogen, and W is either bonded to a hydrogen atom or not, depending on its valence. V'' represents carbon. U is carbon and V is nitrogen, or U is nitrogen and V is carbon, where U, V, and V'' are bonded to a hydrogen atom or not, depending on their valence. R7 and R8 are independently unsubstituted, hydrogen-free, unsubstituted C1-C18 alkyl, cyano, halogenated, or unsubstituted C5-C26 aryl groups, or adjacent R7 or R8 groups, together with atoms in the ring they are bonded to, independently form five- or six-membered C1-C14 alkyl-substituted aryl groups, and n3 and n4 are independent integers between 0 and 5. R1 and R2 are hydrogen, or R1 and R2 together form the following structure: 。 4. The compound of claim 3, having the following structure: Equation VII in: Rv is a C1-C18 alkyl group that is free of hydrogen or unsubstituted, and R7 and R8 are independently hydrogen, unsubstituted C1-C18 alkyl, unsubstituted C5-C26 aryl, halogen, cyano, or Rv and R7, together with the atoms in the rings to which they are bonded, form five- or six-membered C1-C14 alkyl-substituted aryl groups.

5. The compound of claim 3, wherein: Rv is either absent or hydrogen. R7 and R8 are independently hydrogen, isopropyl, tert-butyl, phenyl, fluorine, or cyano, or Rv and R7 together form 。 6. The compound of claim 1, having the following structure: Formula VIII in: (i)M=Cu(I); W=N; Ra=H; U=CH; V=V"=carbon; Rv=H; R7=R8=H; (ii)M=Cu(I); W=N; Ra=H; U=CH; V=V"=carbon; Rv=H; R7=H; R8=CN; (iii) M=Cu(I); W=N; Ra=H; U=CH; V=V"=carbon; Rv=H; R7=R8=tert-butyl; (iv) M=Cu(I); W=N; Ra=H; U=CH; V=V"=carbon; Rv=H; R7=R8=phenyl; (v)M=Cu(I); W=N; Ra=H; U=CH; V=N; V"=carbon; Rv=None; R7=R8=H; (vi)M=Cu(I);W=U=CH;V=V"=carbon;Rv=H;Ra=isopropyl;R7=R8=H; (vii) M=Cu(I); W=N; Ra=H; U=CH; V=V"=carbon; R8=H; Rv and R7 form together ； (viii) M=Cu(I); W=U=CH; Ra=isopropyl; V=V"=carbon; R8=H; Rv and R7 form together ； (ix)M=Cu(I); W=N; Ra=H; U=CH; V=V"=carbon; Rv=H; R7=R8=H; (x)M=Cu(I); W=N; Ra=H; U=CH; V=V"=carbon; Rv=H; R7=H; R8=F; (xi)M=Cu(I); W=N; Ra=H; U=CH; V=V"=carbon; Rv=H; R7=R8=methyl; For (i), (ii), (iii), (iv), (v), (vi), (vii), and (viii), the dashed lines indicate no key, and For (ix), (x), and (xi), the dashed lines indicate the presence of a bond.

7. The compound of claim 1, having the following structure: Where M = Cu(I).

8. A compound having the following structure: Formula I in: The compounds are generally neutral, negatively charged, or positively charged. M represents gold, whose oxidation state is 0, +1, +2, or +3. P' is selected from: ， in: Ra can be hydrogen or isopropyl independently, and Rb is isopropyl. Z has the following structure: in: X1, X2, X3, X4, X5, and X6 are carbon, while X7 and X8 are either carbon or nitrogen. Rx1, Rx2, Rx4, and Rx5 are hydrogen, and Rx3, Rx6, Rx7, and Rx8 are independently hydrogen, halogen, cyano, unsubstituted C1-C18 alkyl, or unsubstituted C5-C26 aryl, wherein when the corresponding X7 or X8 is nitrogen, each Rx7 or Rx8 is absent, or the adjacent Rxn groups, together with the atoms in the ring to which they are bonded, independently form a five- or six-membered C1-C14 alkyl-substituted aryl group, wherein n in the adjacent Rxn groups is a consecutive integer pair of 1 to 4 or 5 to 8.

9. The compound of claim 8, wherein Rx3, Rx6, Rx7 and Rx8 are independently hydrogen, halogen, methyl, cyano, tert-butyl or phenyl.

10. The compound of claim 8, having the following structure: Style VI in: W represents nitrogen. V'' represents carbon. U is carbon and V is nitrogen, or U is nitrogen and V is carbon, where U, V, and V'' are bonded to a hydrogen atom or not, depending on their valence. R7 and R8 are independently unsubstituted, hydrogen-free, unsubstituted C1-C18 alkyl, cyano, halogen, or unsubstituted C5-C26 aryl groups, or adjacent R7 or R8 groups, together with atoms in the ring they are bonded to, independently form five- or six-membered C1-C14 alkyl-substituted aryl groups, and n3 and n4 are independent integers between 0 and 5. R1 and R2 together form the following structure: 。 11. The compound of claim 10, having the following structure: Equation VII in: Rv is a C1-C18 alkyl group that is free of hydrogen or unsubstituted, and R7 and R8 are independently hydrogen, unsubstituted C1-C18 alkyl, unsubstituted C5-C26 aryl, halogen, cyano, or Rv and R7, together with the atoms in the rings to which they are bonded, form five- or six-membered C1-C14 alkyl-substituted aryl groups.

12. The compound of claim 10, wherein: Rv is either absent or hydrogen. R7 and R8 are independently hydrogen, isopropyl, tert-butyl, phenyl, fluorine, or cyano, or Rv and R7 together form 。 13. The compound of claim 8, having the following structure: Formula VIII in: (xxi)M=Au(I); W=N; U=CH; Ra=H; V=V"=carbon; Rv=H; R7=R8=H; (xxii)M=Au(I);W=N;U=CH;Ra=H;V=V"=carbon;Rv=H;R7=R8=tert-butyl; Dashed lines indicate the presence of a bond.

14. The compound of claim 8, having the following structure: Where M = Au(I).

15. A compound having the following structure: Formula I in: The compounds are generally neutral, negatively charged, or positively charged. M represents gold, whose oxidation state is 0, +1, +2, or +3. P' is selected from: or in: Ra can be hydrogen or isopropyl independently, and Rb is isopropyl. Z has the following structure: in: X1, X2, X3, X4, X5, and X6 are carbon, while X7 and X8 are either carbon or nitrogen. Rx1, Rx2, Rx4, and Rx5 are hydrogen; Rx3, Rx7, and Rx8 are independently hydrogen, halogen, cyano, unsubstituted C1-C18 alkyl, or unsubstituted C5-C26 aryl; Rx6 is halogen, cyano, unsubstituted C1-C18 alkyl, or unsubstituted C5-C26 aryl; wherein when the corresponding X7 or X8 is nitrogen, each Rx7 or Rx8 is absent; or the adjacent Rxn groups, together with the atoms in the ring to which they are bonded, independently form a five- or six-membered C1-C14 alkyl-substituted aryl group, wherein n in the adjacent Rxn groups is a consecutive integer pair of 1 to 4 or 5 to 8.

16. The compound of claim 15, wherein Rx3, Rx7 and Rx8 are independently hydrogen, halogen, methyl, cyano, tert-butyl or phenyl, and Rx6 is halogen, methyl, cyano, tert-butyl or phenyl.

17. The compound of claim 15, having the following structure: Style VI in: W represents carbon or nitrogen, and W is either bonded to a hydrogen atom or not, depending on its valence. V'' represents carbon. U is carbon and V is nitrogen, or U is nitrogen and V is carbon, where U, V, and V'' are bonded to a hydrogen atom or not, depending on their valence. R7 is an unsubstituted or unsubstituted C1-C18 alkyl, cyano, halogen, or unsubstituted C5-C26 aryl group, or an adjacent R7 group or an adjacent R8 group, together with atoms in the ring to which they are bonded, independently form a five- or six-membered C1-C14 alkyl-substituted aryl group. R8 is an unsubstituted, hydrogen-free, unsubstituted C1-C18 alkyl, cyano, halogen, or unsubstituted C5-C26 aryl group, or an adjacent R7 group or an adjacent R8 group, together with atoms in the ring to which they are bonded, independently forming a five- or six-membered C1-C14 alkyl-substituted aryl group, and n3 and n4 are independent integers between 0 and 5. R1 and R2 are hydrogen.

18. The compound of claim 17, having the following structure: Equation VII in: Rv is a C1-C18 alkyl group that is free of hydrogen or unsubstituted, and R8 can be hydrogen, an unsubstituted C1-C18 alkyl group, an unsubstituted C5-C26 aryl group, a halogen, or a cyano group. R7 is an unsubstituted C1-C18 alkyl, an unsubstituted C5-C26 aryl, a halogen, a cyano, or Rv and R7, together with the atoms in the rings to which they are bonded, form five- or six-membered C1-C14 alkyl-substituted aryl groups.

19. The compound of claim 17, wherein: Rv is either absent or hydrogen. R8 can be hydrogen, isopropyl, tert-butyl, phenyl, fluorine, or cyano. R7 is isopropyl, tert-butyl, phenyl, fluorine, or cyano, or Rv and R7 together form 。 20. The compound of claim 15, having the following structure: Formula VIII in: (xvii)M=Au(I); W=N; Ra=H; U=CH; V=V"=carbon; Rv=H; R7=R8=CN; (xviii) M=Au(I); W=N; Ra=hydrogen; U=CH; V=V"=carbon; R8=H; Rv and R7 form together ； (xix)M=Au(I); W=U=CH; Ra=isopropyl; V=V"=carbon; Rv=H; R7=R8=tert-butyl; A dashed line indicates that there is no key.

21. The compound of claim 15, having the following structure: Where M = Au(I).

22. A compound having the following structure: Formula VIII in: (xiii) M=Au(I); W=N; Ra=H; U=CH; V=carbon; Rv=H; V"=carbon; R7=H; R8=CN; (xiv)M=Au(I); W=N; Ra=H; U=N; V=carbon; Rv=H; V"=carbon; R7=R8=H; (xvi)M=Au(I);W=N;Ra=H;U=CH;V=N;Rv=none;V"=carbon;R7=R8=H; A dashed line indicates that there is no key.

23. An organic electronic component comprising a compound according to any one of claims 1 to 22.

24. The organic electronic element of claim 23, wherein the organic electronic element is an organic light-emitting diode (OLED) or a light-emitting electrochemical cell (LEEC).

25. The organic electronic device of claim 23, wherein the compound is in the light-emitting layer.

26. The organic electronic component of claim 23 further includes an anode, a cathode, a hole transport region, and an electron transport region. The hole transport region includes a hole injection layer and / or a hole transport layer, and optionally an electron blocking layer. The electron transport region includes an electron transport layer and / or an electron injection layer, and optionally a hole blocking layer. The light-emitting layer is located between the anode and the cathode. The hole transport region is located between the anode and the light-emitting layer, and the electron transport region is located between the cathode and the light-emitting layer.

27. The organic electronic component of claim 25, wherein the light-emitting layer is manufactured by vacuum deposition, spin coating, or ink printing.

28. A light-emitting layer comprising the compound of any one of claims 1 to 22.

29. A light-emitting layer comprising a compound of any one of claims 1 to 22 and a pure organic emitter, wherein the compound acts as a sensitizer to transfer energy to the pure organic light-emitting layer.

30. A light-emitting layer comprising a compound of any one of claims 1 to 22 and a pure organic emitter, wherein the compound has a higher singlet state than the pure organic emitter.

31. A light-emitting layer comprising a compound of any one of claims 1 to 22 and a pure organic emitter, wherein the compound acts as a sensitizer to transfer energy to the pure organic emitter exhibiting thermally activated delayed fluorescence.

32. A light-emitting layer comprising a compound of any one of claims 1 to 22 and a pure organic emitter, wherein the compound acts as a sensitizer to transfer energy to the boron-based pure organic emitter.

33. An OLED comprising the light-emitting layer of any one of claims 28 to 32.

34. A device comprising the OLED of claim 33, wherein the device is selected from fixed visual display units, mobile visual display units, lighting units, clothing, decorations, wearable devices, wallpaper, tablet computers, and laptop computers.

Images