Patent Publication Number: US-2023165135-A1

Title: d10 METAL CARBENE COMPLEXES FOR OLED APPLICATIONS

Description:
CROSS-REFERENCE TO RELATED APPLICATION 
     This application claims benefit of and priority to U.S. Provisional Application No. 63/282,496 filed Nov. 23, 2021, which is incorporated herein by reference in its entirety. 
    
    
     FIELD OF THE INVENTION 
     The disclosed invention is generally in the field of luminescent d10 metal carbene complexes, particularly d10 metal carbene complexes containing (i) a pyrazine-fused N-heterocyclic carbene ligand or a pyridine-fused N-heterocyclic carbene ligand and (ii) a carbazole ligand or an alpha-, beta-gamma-, or delta carboline ligand, and the use of these complexes in organic light-emitting devices (OLEDs). 
     BACKGROUND OF THE INVENTION 
     Transition metal complexes have gained significant interest in commercial and academic settings as molecular probes, catalysts, and luminescent materials. As luminescent materials, transition metal complexes are increasingly being explored as potential alternatives to pure organic-based materials due to their potential for improved luminescence efficiency and device stability, compared to pure organic-based materials. 
     Currently, cyclometalated iridium(III) and Pt(II) phosphors are among the most competitive candidates in commercial OLED emitters. Nonetheless, the development of metal-based or organic thermally activated delayed fluorescence (TADF) emitters still lag behinds, mainly because of their lower stability that can affect device lifetimes. The device performance and operational stability/lifetime of metal-based OLEDs must be enhanced for practical applications. Several studies have described d10 complexes for use as OLED emitters. These include U.S. Pat. No. 9,773,986 to Thompson, et al.; European Patent Application Publication 3,489,243 by Thompson, et al.; U.S. Patent Application Publication 2015/0108451 by Thompson, et al., and U.S. Patent Application Publication 2019/0161504 by Thompson, et al.; and CN112794863. Nonetheless, these studies do not report the results of device lifetime. Additional studies include complexes of Cu(I), Ag(I), or Au(I), involving carbene ligands and carbazoles, such as: 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 of the complexes showed phosphorescent character, leading to lower radiative decay rates. For example, the complexes IPr-Cu-Cz and IMes-Cu-Cz (Angew. Chem. Int. Ed. 2020, 59,8210-8217) showed long-lived room-temperature phosphorescence with lifetime in the millisecond range. 
     Accordingly, there remains a need to develop improved and efficient transition metal complexes so that OLED-containing products can have improved efficiencies. 
     Therefore, is an object of the present invention to provide new and improved luminescent transition metal two-coordinate complexes containing a d10 metal. 
     SUMMARY OF THE INVENTION 
     Described are two-coordinated d10 metal carbene complexes containing (i) Cu(I), Ag(I), or Au(I), (ii) a pyrazine-fused N-heterocyclic carbene (NHC) ligand or a pyridine-fused N-heterocyclic carbene 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 these compounds can be controlled by TADF. The emission colors of these compounds can also be tuned by using carbazoles, pyrido[2,3-b]indoles, or pyrido[3,4-b]indoles with varying donor strength. 
     The compounds have a structure: 
     
       
         
         
             
             
         
       
     
     wherein: 
     D is carbon, 
     T, J, and W are independently carbon or nitrogen, wherein at least one of T, J, and W is nitrogen, wherein when T is carbon, J is nitrogen, or when T is nitrogen, J is carbon, and T, J, and W are bonded to one or no hydrogen atom according to valency, 
     each Ra is independently hydrogen, unsubstituted alkyl, or substituted alkyl, 
     each Rb is independently unsubstituted alkyl, or substituted alkyl, 
     X and Y are nitrogen, 
     L is absent or a single bond, 
     CY3 and CY4 are independently unsubstituted aryl, substituted aryl, unsubstituted heteroaryl, substituted heteroaryl, substituted C 3 -C 20  cycloalkenyl, unsubstituted C 3 -C 20  cycloalkenyl, or a fused combination thereof, and 
     R 1  and R 2  are hydrogen, or R 1 , J, D, and R 2  together form an unsubstituted aryl, substituted aryl, unsubstituted heteroaryl, or substituted heteroaryl. 
     In some forms, the compounds have a structure: 
     
       
         
         
             
             
         
       
     
     wherein: 
     (i) M=Cu(I); W=N; Ra=H; U=CH; V=V″=carbon; Rv=H; R 7 =R 8 =H; 
     (ii) M=Cu(I); W=N; Ra=H; U=CH; V=V″=carbon; Rv=H; R 7 =H; R 8 =CN; 
     (iii) M=Cu(I); W=N; Ra=H; U=CH; V=V″=carbon; Rv=H; R 7 =R 8 =tert-butyl; 
     (iv) M=Cu(I); W=N; Ra=H; U=CH; V=V″=carbon; Rv=H; R 7 =R 8 =phenyl; 
     (v) M=Cu(I); W=N; Ra=H; U=CH; V=N; V″=carbon; Rv=absent; R 7 =R 8 =H; (vi) M=Cu(I); W=U=CH; V=V″=carbon; Rv=H; Ra=iso-propyl; R 7 =R 8 =H; 
     (vii) M=Cu(I); W=N; Ra=H; U=CH; V=V″=carbon; R 8 =H; Rv and R 7  together form 
     
       
         
         
             
             
         
       
     
     (viii) M=Cu(I); W=U=CH; Ra=iso-propyl; V=V″=carbon; R 8 =H; Rv and R 7  together form 
     
       
         
         
             
             
         
       
     
     (ix) M=Cu(I); W=N; Ra=H; U=CH; V=V″=carbon; Rv=H; R 7 =R 8 =H; 
     (x) M=Cu(I); W=N; Ra=H; U=CH; V=V″=carbon; Rv=H; R 7 =H; R 8 =F; 
     (xi) M=Cu(I); W=N; Ra=H; U=CH; V=V″=carbon; Rv=H; R 7 =R 8 =methyl; 
     (xii) M=Au(I); W=N; Ra=H; U=CH; V=carbon; Rv=H; V″=carbon; R 7 =R 8 =H; 
     (xiii) M=Au(I); W=N; Ra=H; U=CH; V=carbon; Rv=H; V″=carbon; R 7 =H, R 8 =CN; 
     (xiv) M=Au(I); W=N; Ra=H; U=N; V=carbon; Rv=H; V″=carbon; R 7 =R 8 =H; 
     (xv) M=Au(I); W=U=CH; V=carbon; Rv=H; ; Ra=iso-propyl; V″=carbon; R 7 =R 8 =H; 
     (xvi) M=Au(I); W=N; Ra=H; U=CH; V=N; Rv=absent; V″=carbon; R 7 =R 8 =H; 
     (xvii) M=Au(I); W=N; Ra=H; U=CH; V=V″=carbon; Rv=H; R 7 =R 8 =CN; 
     (xviii) M=Au(I); W=N; Ra=hydrogen; U=CH; V=V″=carbon; R 8 =H; Rv and R 7  together form 
     
       
         
         
             
             
         
       
     
     (xix) M=Au(I); W=U=CH; Ra=iso-propyl; V=V″=carbon; Rv=H; R 7 =R 8 =tert-butyl; 
     (xx) M=Au(I); W=U=CH; Ra=iso-propyl; V=V″=carbon; Rv=H; R 7 =H; R 8 =F; 
     (xxi) M=Au(I); W=N; U=CH; Ra=H; V=V″=carbon; Rv=H; R 7 =R 8 =H; 
     (xxii) M=Au(I); W=N; U=CH; Ra=H; V=V″=carbon; Rv=H; R 7 =R 8 =tert-butyl; 
     (xxiii) M=Ag(I); W=N; U=CH; Ra=H; V=V″=carbon; Rv=H; R 7 =R 8 =H; 
     for (i), (ii), (iii), (iv), (v), (vi), (vii), (viii), (xii), (xiii), (xiv), (xv), (xvi), (xvii), (xviii), (xix), (xx), and (xxiii), the dashed lines denote the absence of bonds, and 
     for (ix), (x), (xi), xxi, and xxii, the dashed lines denote the presence of bonds. 
     The disclosed compounds can be included in organic light-emitting devices, for use in commercial applications. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         FIG.  1    shows chemical structures of metal carbene complexes denoted Cu1, Cu2, Cu3, Cu4, Cu5, Cu6, Cu1, Cu8, Cu9, Cu10, Cu11, Au1, Au2, Au3, Au4, Au5, Au6, Au7, Au8, Au9, Au10, Au11, and Ag1. 
         FIGS.  2 A,  2 B,  2 C,  2 D,  2 E, and  2 F  show the crystal structures of Au1, Au4, Au8, Au9, Cu3, and Cu6, respectively, shown in  FIG.  1   . 
         FIGS.  3 A- 3 D  are line graphs showing electroluminescent spectra and performance characteristics of Cu1-based devices with doping concentration of 2-8wt/wt %. Device structure: ITO/HAT-CN (5 nm)/TAPC (40 nm)/TCTA (10 nm)/TCTA: TPBi: Cu1 (20 nm)/TPBi (50 nm)/LiF (1 nm)/Al (100 nm). 
         FIGS.  4 A- 4 D  are line graphs showing electroluminescent spectra and performance characteristics of devices of Cu2 with doping concentration of 2-6 wt/wt %. Device structure: ITO/HAT-CN (5 nm)/TAPC (40 nm)/TCTA (10 nm)/TCTA: DPEPO: Cu2 (20 nm)/DPEPO (10 nm)/TPBi (40 nm)/LiF (1 nm)/Al (100 nm). 
         FIGS.  5 A- 5 D  are line graphs showing electroluminescent spectra and performance characteristics of devices of Cu3 with doping concentration of 2-6 wt/wt %. Device structure: ITO/HAT-CN (5 nm)/TAPC (40 nm)/TCTA (10 nm)/TCTA: TPBi: Cu3 (20 nm)/TPBi (50 nm)/LiF (1 nm)/Al (100 nm). 
         FIGS.  6 A- 6 D  are line graphs showing electroluminescent spectra and performance characteristics of devices of Au1 with doping concentration of 2-6 wt/wt %. Device structure: ITO/HAT-CN (5 nm)/TAPC (40 nm)/TCTA (10 nm)/TCTA: TPBi: Au1 (20 nm)/TPBi (50 nm)/LiF (1 nm)/Al (100 nm). 
         FIGS.  7 A- 7 D  are line graphs showing electroluminescent spectra and performance characteristics of devices of Au2 with doping concentration of 2-6 wt/wt %. Device structure(I): ITO/HAT-CN (5 nm)/TAPC (40 nm)/TCTA (10 nm)/TCTA: TPBi: Au2 (20 nm)/TPBi (50 nm)/LiF (1 nm)/Al (100 nm). 
         FIGS.  8 A- 8 D  are line graphs showing electroluminescent spectra and performance characteristics of devices of Au2 with doping concentration of 2-8 wt/wt %. Device structure (II): ITO/HAT-CN (5 nm)/TAPC (40 nm)/TCTA (10 nm)/TCTA: DPEPO: Au2 (20 nm)/DPEPO (10 nm)/TPBi (40 nm)/LiF (1 nm)/Al (100 nm). 
         FIG.  9    is a line graph showing the emission spectra of Cu4. 
         FIG.  10    is a line graph showing the emission spectra of Au3. 
         FIG.  11    is a line graph showing the emission spectra of Cu5. 
         FIGS.  12 A and  12 B  are line graphs showing the emission spectra of Cu6 and Au4. 
         FIGS.  13 A- 13 C  are line graphs showing device data for Cu2 in Table 5b. EL spectra and performance characteristics of devices of Cu2 with doping concentration of 2 wt/wt %. Device structure: ITO/HAT-CN (5 nm)/PT-301 (160 nm)/PT-603I (5 nm)/Cu2: LLP604 (20 nm)/PT74M (5 nm)/LET321: Liq (1:1, 25 nm)/Liq (1 nm)/Al (100 nm). 
         FIGS.  14 A- 14 D  are line graphs showing the EL spectra and performance characteristics of devices of Cu3 with doping concentration of 2-6 wt/wt %. Device structure (II): ITO/HAT-CN (5 nm)/PT-301 (160 nm)/EB (5 nm)/Cu3: RH (40 nm)/HB (5 nm)/ZADN: Liq (35:65, 35 nm)/Liq (1 nm)/Al (100 nm). 
         FIGS.  15 A- 15 D  are line graphs showing the EL spectra and performance characteristics of devices of Cu4 with doping concentration of 2-6 wt/wt %. Device structure (I): ITO/HAT-CN (5 nm)/TAPC (40 nm)/TCTA (10 nm)/TCTA: TPBi: Cu4 (20 nm)/TPBi (50 nm)/LiF (1 nm)/Al (100 nm). 
         FIGS.  16 A- 16 D  are line graphs showing the EL spectra and performance characteristics of devices of Cu4 with doping concentration of 2-6 wt/wt %. Device structure (II): ITO/HAT-CN (5 nm)/PT-301 (160 nm)/PT-603I (5 nm)/Cu4: LLP604 (20 nm)/PT74M (5 nm)/LET321: Liq (1:1, 25 nm)/Liq (1 nm)/Al (100 nm). 
         FIGS.  17 A- 17 D  are line graphs showing the EL spectra and performance characteristics of devices of Au2 with doping concentration of 2-8 wt/wt %. Device structure (III): ITO/HAT-CN (5 nm)/PT-301 (160 nm)/PT-603I (5 nm)/Au2: LLP604 (20 nm)/PT74M (5 nm)/LET321: Liq (1:1, 25 nm)/Liq (1 nm)/Al (100 nm). 
         FIG.  18    is a line graph showing the emission spectra of Cu1 (in MCP film). 
         FIG.  19    is a line graph showing the emission spectra of Cu8 (in MCP film). 
         FIG.  20    is a line graph showing the emission spectra of Cu9 (in degassed toluene and MCP film). 
         FIG.  21    is a line graph showing the emission spectra of Au7 (2 wt/wt % in PMMA film). 
         FIGS.  22 A- 22 D  are line graphs showing the EL spectra and performance characteristics of devices of Cu6 in TCTA:DPEPO co-host, with doping concentration of 2-6 wt/wt %. Device structure: ITO/HAT-CN (5 nm)/TAPC (40 nm)/TCTA (10 nm)/TCTA: DPEPO: Cu6 (20 nm)/DPEPO (10 nm)/TPBi (40 nm)/LiF (1.2 nm)/Al (100 nm). 
         FIGS.  23 A- 23 D  are line graphs showing the EL spectra and performance characteristics of vapor-deposited hyper-fluorescence OLED with Cu6 and v-DABNA in mCBP. Device structure: ITO/HAT-CN (10 nm)/BPBPA (120 nm)/mCBP (10 nm)/mCBP: Cu6: v-DABNA (20 nm)/SF3-TRz (5 nm)/SF3-TRz: Liq (1:1, 25 nm)/Liq (2 nm)/Al (100 nm). 
         FIGS.  24 A- 24 D  are line graphs showing the EL spectra and performance characteristics of Cu7 in DMIC-Cz: DMIC-Trz co-host, with doping concentration of 2-6 wt/wt %. Device structure: ITO/HAT-CN (10 nm)/BPBOA (80 nm)/FSF4A (5 nm)/DMIC-Cz: DMIC-Trz: Cu7 (30 nm)/ANT-Biz (5 nm)/ANT-Biz: Liq (25 nm)/Liq (2 nm)/Al (100 nm). 
         FIGS.  25 A- 25 D  are line graphs showing the EL spectra and performance characteristics of vapor-deposited hyper-fluorescence OLED with Cu7 and MR-R in RH. Device structure: ITO/HAT-CN (10 nm)/HT (40 nm)/EB (5 nm)/Cu7: MR-R: RH (40 nm)/HB (5 nm)/ZADN: Liq (35:65) (35 nm)/Liq (2 nm)/Al (100 nm). 
         FIGS.  26 A- 26 D  are line graphs showing the EL spectra and performance characteristics of vapor-deposited hyper-fluorescence OLED with Au3 and BN-2 in mCBP. Device structure: ITO/HAT-CN (5 nm)/TAPC (40 nm)/mCBP (10 nm)/Au3: BN-2: mCBP (20 nm)/PPF (10nm)/TmPyPb (40 nm)/LiF (1.2 nm)/Al (100 nm). 
         FIGS.  27 A- 27 D  are line graphs showing the EL spectra and performance characteristics of Au5 in mCBP:CzSiTrz co-host, with doping concentration 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). 
         FIG.  28    is a line graph showing the emission spectra of Au10 (in MCP film). 
         FIG.  29    is a line graph showing the emission spectra of Au11 (in MCP film). 
     
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     I. Definitions 
     “Alkyl” includes straight and branched chain alkyl groups, as well as cycloalkyl groups with alkyl groups having a cyclic structure. Preferred alkyl groups are those containing between one to eighteen carbon atoms and includes methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, and other similar compounds. In addition, the alkyl group may be optionally substituted with one or more substituents selected from hydrogen atom, deuterium atom, formaldehyde, cyano, alkylalkynyl, substituted alkylalkynyl, arylalkynyl, substituted arylalkynyl, heteroarylalkynyl, substituted heteroarylalkynyl, condensed polycyclic, substituted condensed polycyclic, aryl, alkyl, heteroaryl, nitro, trifluoromethane, cyano, arylether, alkylether, heteroarylether, diarylamine, dialkylamine, diheteroarylamine, diarylborane, triarylsilane, trialkylsilane, alkenyl, alkylaryl, cycloalkyl, haloformyl, hydroxyl, aldehyde, carboxamide, amine, amino, alkoxy, azo, benzyl, carbonate ester, carboxylate, carboxyl, ketamine, isocyanate, isocyanide, isothiocyanate, nitrile, nitro, nitroso, phosphine, phosphate, phosphono, pyridyl, sulfonyl, sulfo, sulfinyl, sulfhydryl, halo, aryl, substituted aryl, heteroaryl, substituted heteroaryl, heterocyclic and derivatives thereof. It will be understood by those skilled in the art that the moieties substituted on the hydrocarbon chain can themselves be substituted, if appropriate. For instance, the substituents of a substituted alkyl may include halogen, hydroxy, nitro, thiols, amino, azido, imino, amido, phosphoryl (including phosphonate and phosphinate), sulfonyl (including sulfate, sulfonamido, sulfamoyl and sulfonate), and silyl groups, as well as ethers, alkylthios, carbonyls (including ketones, aldehydes, carboxylates, and esters), haloalkyls, —CN and the like. Cycloalkyls can be substituted in the same manner. 
     “Substituted,” as used herein, refers to all permissible substituents of the compounds or functional groups described herein. In the broadest sense, the permissible substituents include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, aromatic and nonaromatic substituents of organic compounds. Illustrative substituents include, but are not limited to, halogens, hydroxyl groups, or any other organic groupings containing any number of carbon atoms, preferably 1-14 carbon atoms, and optionally include one or more heteroatoms such as oxygen, sulfur, or nitrogen grouping in linear, branched, or cyclic structural formats. Representative substituents include alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, phenyl, substituted phenyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, halo, hydroxyl, alkoxy, substituted alkoxy, phenoxy, substituted phenoxy, aroxy, substituted aroxy, alkylthio, substituted alkylthio, phenylthio, substituted phenylthio, arylthio, substituted arylthio, cyano, isocyano, substituted isocyano, oxo (═O), carbonyl, substituted carbonyl, carboxyl, substituted carboxyl, amino, substituted amino, amido, substituted amido, sulfonyl, substituted sulfonyl, sulfonic acid, phosphoryl, substituted phosphoryl, phosphonyl, substituted phosphonyl, polyaryl, substituted polyaryl, cyclic (such as C 3 -C 20  cyclic), substituted cyclic (such as substituted C 3 -C 20  cyclic), heterocyclic, substituted heterocyclic, amino acid, poly(lactic-co-glycolic acid), peptide, polypeptide, deuterium, unsubstituted alkylalkynyl, substituted alkylalkynyl, unsubstituted arylalkynyl, substituted arylalkynyl, unsubstituted heteroarylalkynyl, substituted heteroarylalkynyl, trihaloalkyl (trifluoromethyl), unsubstituted heteroarylether, substituted heteroarylether, unsubstituted diarylamino, substituted diarylamino, unsubstituted dialkylamino, substituted dialkylamino, unsubstituted diheteroarylamino, substituted diheteroarylamino, unsubstituted diarylboraneyl, substituted diarylboraneyl, unsubstituted triarylsilyl, substituted triarylsilyl, unsubstituted trialkylsilyl, substituted trialkylsilyl, azo, carbonate ester, ketamine, nitro, nitroso, phosphino, pyridyl, NRR′, SR, C(O)R, COOR, C(O)NR, SOR, and BRR&#39; groups, wherein and R and R′ are independently selected from hydrogen atom, deuterium atom, formaldehyde, cyano, alkylalkynyl, substituted alkylalkynyl, arylalkynyl, substituted arylalkynyl, heteroarylalkynyl, substituted heteroarylalkynyl, condensed polycyclic, substituted condensed polycyclic, aryl, alkyl, heteroaryl, nitro, trifluoromethane, cyano, arylether, alkylether, heteroarylether, diarylamine, dialkylamine, diheteroarylamine, diarylborane, triarylsilane, trialkylsilane, alkenyl, alkylaryl, cycloalkyl, haloformyl, hydroxyl, aldehyde, carboxamide, amine, amino, alkoxy, azo, benzyl, carbonate ester, carboxylate, carboxyl, ketamine, isocyanate, isocyanide, isothiocyanate, nitrile, nitro, nitroso, phosphine, phosphate, phosphono, pyridyl, sulfonyl, sulfo, sulfinyl, sulfhydryl, halo, aryl, substituted aryl, heteroaryl, substituted heteroaryl, and heterocyclic groups. Such alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, phenyl, substituted phenyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, halo, hydroxyl, alkoxy, substituted alkoxy, phenoxy, substituted phenoxy, aroxy, substituted aroxy, alkylthio, substituted alkylthio, phenylthio, substituted phenylthio, arylthio, substituted arylthio, cyano, isocyano, substituted isocyano, carbonyl, substituted carbonyl, carboxyl, substituted carboxyl, amino, substituted amino, amido, substituted amido, sulfonyl, substituted sulfonyl, sulfonic acid, phosphoryl, substituted phosphoryl, phosphonyl, substituted phosphonyl, polyaryl, substituted polyaryl, cyclic (such as C 3 -C 20  cyclic), substituted cyclic (such as substituted C 3 -C 20  cyclic), heterocyclic, substituted heterocyclic, amino acid, poly(lactic-co-glycolic acid), peptide, polypeptide, deuterium, substituted alkylalkynyl, substituted alkylalkynyl, unsubstituted arylalkynyl, substituted arylalkynyl, unsubstituted heteroarylalkynyl, substituted heteroarylalkynyl, trihaloalkyl (trifluoromethyl), unsubstituted heteroarylether, substituted heteroarylether, unsubstituted diarylamino, substituted diarylamino, unsubstituted dialkylamino, substituted dialkylamino, unsubstituted diheteroarylamino, substituted diheteroarylamino, unsubstituted diarylboraneyl, substituted diarylboraneyl, unsubstituted triarylsilyl, substituted triarylsilyl, unsubstituted trialkylsilyl, substituted trialkylsilyl, azo, carbonate ester, ketamine, nitro, nitroso, phosphide, phosphino, and pyridyl groups can be further substituted. 
     The term “heteroatom” as used herein includes, but is not limited to, S, O, N, P, Se, Te, As, Sb, Bi, B, Si, Ge, Sn and Pb. Heteroatoms such as nitrogen may have hydrogen substituents and/or any permissible substituents of organic compounds described herein which satisfy the valences of the heteroatoms. It is understood that “substitution” or “substituted” includes the implicit proviso that such substitution is in accordance with 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 transformation such as by rearrangement, cyclization, elimination, etc. 
     The term “alkenyl” as used herein is a hydrocarbon group having, for example, from 2 to 24 carbon atoms and a structural formula containing at least one carbon-carbon double bond. Asymmetric structures such as (AB)C=C(CD) are intended to include both the E and Z isomers. This may be presumed in structural formulae herein wherein an asymmetric alkene is present, or it may be explicitly indicated by the bond symbol C. 
     The term “alkynyl group” as used herein is a hydrocarbon group having, for example, 2 to 24 carbon atoms and a structural formula containing at least one carbon-carbon triple bond. 
     The term “aryl” as used herein is any C 5 -C 26  carbon-based aromatic group, fused aromatic, fused heterocyclic, or biaromatic ring systems. Broadly defined, “aryl,” as used herein, includes 5-, 6-, 7-, 8-, 9-, 10-, 14-, 18-, and 24-membered single-ring aromatic groups, including, but not limited to, benzene, naphthalene, anthracene, phenanthrene, chrysene, pyrene, corannulene, coronene, etc. “Aryl” further encompasses polycyclic ring systems having two or more cyclic rings in which two or more carbons are common to two adjoining rings (i.e., “fused rings”) wherein at least one of the rings is aromatic, e.g., the other cyclic ring or rings can be cycloalkyls, cycloalkenyls, cycloalkynyls, aryls and/or heterocycles. The aryl group can be substituted with one or more groups including, but not limited to, alkyl, alkynyl, alkenyl, aryl, halide, nitro, amino, ester, ketone, aldehyde, hydroxy, carboxylic acid, or alkoxy. 
     The term “substituted aryl” refers to an aryl group, wherein one or more hydrogen atoms on one or more aromatic rings are substituted with one or more substituents including, but not limited to, halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, alkoxy, carbonyl (such as a ketone, aldehyde, carboxyl, alkoxycarbonyl, formyl, or an acyl), silyl, ether, ester, thiocarbonyl (such as a thioester, a thioacetate, or a thioformate), alkoxyl, phosphoryl, phosphate, phosphonate, phosphinate, amino (or quarternized amino), amido, amidine, imine, cyano, nitro, azido, sulfhydryl, imino, alkylthio, sulfate, sulfonate, sulfamoyl, sulfonamido, sulfonyl, heterocyclyl, alkylaryl, haloalkyl (such as CF3, —CH 2 -CF 3 , —CCl 3 ), —CN, aryl, heteroaryl, and combinations thereof. 
     “Heterocycle,” “heterocyclic” and “heterocyclyl” are used interchangeably, and refer to a cyclic radical attached via a ring carbon or nitrogen atom of a monocyclic, bicyclic, or tricyclic ring containing 3-14 ring atoms, and preferably from 5-6 ring atoms, consisting of carbon and one to four heteroatoms each selected from the group consisting of non-peroxide oxygen, sulfur, and N(Y) wherein Y is absent or is H, O, C 1 -C 10  alkyl, phenyl or benzyl, and optionally containing 1-3 double bonds and optionally substituted with one or more substituents. Heterocyclyl are distinguished from heteroaryl by definition. Examples of heterocycles include, but are not limited to piperazinyl, piperidinyl, piperidonyl, 4-piperidonyl, dihydrofuro[2,3-b]tetrahydrofuran, morpholinyl, piperazinyl, piperidinyl, piperidonyl, 4-piperidonyl, piperonyl, pyranyl, 2H-pyrrolyl, 4H-quinolizinyl, quinuclidinyl, tetrahydrofuranyl, 6H-1,2,5-thiadiazinyl. Heterocyclic groups can optionally be substituted with one or more substituents as defined above for alkyl and aryl. 
     The term “heteroaryl” refers to C 5 -C 26 -membered aromatic, fused aromatic, biaromatic ring systems, or combinations thereof, in which one or more carbon atoms on one or more aromatic ring structures have been substituted with a heteroatom. Suitable heteroatoms include, but are not limited to, oxygen, sulfur, and nitrogen. Broadly defined, “heteroaryl,” as used herein, includes 5-, 6-, 7-, 8-, 9-, 10-, 14-, 18-, and 24-membered single-ring aromatic groups that may include from one to four heteroatoms, for example, pyrrole, furan, thiophene, imidazole, oxazole, thiazole, triazole, tetrazole, pyrazole, pyridine, pyrazine, pyridazine and pyrimidine, and the like. The heteroaryl group may also be referred to as “aryl heterocycles” or “heteroaromatics.” “Heteroaryl” further encompasses polycyclic ring systems having two or more rings in which two or more carbons are common to two adjoining rings (i.e., “fused rings”) wherein at least one of the rings is heteroaromatic, e.g., the other cyclic ring or rings can be cycloalkyls, cycloalkenyls, cycloalkynyls, aryls, heterocycles, or combinations thereof. Examples of heteroaryl rings include, but are not limited to, benzimidazolyl, benzofuranyl, benzothiofuranyl, benzothiophenyl, benzoxazolyl, benzoxazolinyl, benzthiazolyl, benztriazolyl, benztetrazolyl, benzisoxazolyl, benzisothiazolyl, benzimidazolinyl, carbazolyl, 4aH-carbazolyl, carbolinyl, chromanyl, chromenyl, cinnolinyl, decahydroquinolinyl, 2H,6H-1,5,2-dithiazinyl, furanyl, furazanyl, imidazolidinyl, imidazolinyl, imidazolyl, 1H-indazolyl, indolenyl, indolinyl, indolizinyl, indolyl, 3H-indolyl, isatinoyl, isobenzofuranyl, isochromanyl, isoindazolyl, isoindolinyl, isoindolyl, isoquinolinyl, isothiazolyl, isoxazolyl, methylenedioxyphenyl, naphthyridinyl, octahydroisoquinolinyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,3,4-oxadiazolyl, oxazolidinyl, oxazolyl, oxindolyl, pyrimidinyl, phenanthridinyl, phenanthrolinyl, phenazinyl, phenothiazinyl, phenoxathinyl, phenoxazinyl, phthalazinyl, pteridinyl, purinyl, pyrazinyl, pyrazolidinyl, pyrazolinyl, pyrazolyl, pyridazinyl, pyridooxazole, pyridoimidazole, pyridothiazole, pyridinyl, pyridyl, pyrimidinyl, pyrrolidinyl, pyrrolinyl, pyrrolyl, quinazolinyl, quinolinyl, quinoxalinyl, tetrahydroisoquinolinyl, tetrahydroquinolinyl, tetrazolyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,2,5-thiadiazolyl, 1,3,4-thiadiazolyl, thianthrenyl, thiazolyl, thienyl, thienothiazolyl, thienooxazolyl, thienoimidazolyl, thiophenyl and xanthenyl. One or more of the rings can be substituted as defined below for “substituted heteroaryl”. 
     The term “substituted heteroaryl” refers to a heteroaryl group in which one or more hydrogen atoms on one or more heteroaromatic rings are substituted with one or more substituents including, but not limited to, halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, alkoxy, carbonyl (such as a ketone, aldehyde, carboxyl, alkoxycarbonyl, formyl, or an acyl), silyl, ether, ester, thiocarbonyl (such as a thioester, a thioacetate, or a thioformate), alkoxyl, phosphoryl, phosphate, phosphonate, phosphinate, amino (or quarternized amino), amido, amidine, imine, cyano, nitro, azido, sulfhydryl, imino, alkylthio, sulfate, sulfonate, sulfamoyl, sulfonamido, sulfonyl, heterocyclyl, alkylaryl, haloalkyl (such as CF3, —CH 2 -CF 3 , —CCl 3 ), —CN, aryl, heteroaryl, and combinations thereof. 
     The term “substituted alkenyl” refers to alkenyl moieties having one or more substituents replacing one or more hydrogen atoms on one or more carbons of the hydrocarbon backbone. Such substituents include, but are not limited to, halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (such as a carboxyl, alkoxycarbonyl, formyl, or an acyl), silyl, ether, ester, thiocarbonyl (such as a thioester, a thioacetate, or a thioformate), alkoxyl, phosphoryl, phosphate, phosphonate, phosphinate, amino (or quarternized amino), amido, amidine, imine, cyano, nitro, azido, sulfhydryl, alkylthio, sulfate, sulfonate, sulfamoyl, sulfonamido, sulfonyl, heterocyclyl, alkylaryl, haloalkyl, —CN, aryl, heteroaryl, and combinations thereof. 
     The term “substituted alkynyl” refers to alkynyl moieties having one or more substituents replacing one or more hydrogen atoms on one or more carbons of the hydrocarbon backbone. Such substituents include, but are not limited to, halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (such as a carboxyl, alkoxycarbonyl, formyl, or an acyl), silyl, ether, ester, thiocarbonyl (such as a thioester, a thioacetate, or a thioformate), alkoxyl, phosphoryl, phosphate, phosphonate, phosphinate, amino (or quarternized amino), amido, amidine, imine, cyano, nitro, azido, sulfhydryl, alkylthio, sulfate, sulfonate, sulfamoyl, sulfonamido, sulfonyl, heterocyclyl, alkylaryl, haloalkyl, —CN, aryl, heteroaryl, and combinations thereof. 
     The term “cycloalkyl” as used herein is a non-aromatic carbon-based ring composed of at least three carbon atoms. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc. The term “heterocycloalkyl group” is a cycloalkyl group as defined above where at least one of the carbon atoms of the ring is substituted with a heteroatom such as, but not limited to, nitrogen, oxygen, sulphur, or phosphorus. 
     The term “aralkyl” as used herein is an aryl group having an alkyl, alkynyl, or alkenyl group as defined above attached to the aromatic group. An example of an aralkyl group is a benzyl group. 
     “Carbonyl,” as used herein, is art-recognized and includes such moieties as can be represented by the general formula: 
     
       
         
         
             
             
         
       
     
     wherein X is a bond, or represents an oxygen or a sulfur, and R represents a hydrogen, a substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted arylalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl, —(CH 2 ) m —R″, or a pharmaceutical acceptable salt, R′ represents a hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted arylalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl or —(CH2) m R″; R″ represents a hydroxy group, substituted or unsubstituted carbonyl group, an aryl, a cycloalkyl ring, a cycloalkenyl ring, a heterocycle, or a polycycle; and m is zero or an integer ranging from 1 to 8. Where X is oxygen and R is defined as above, the moiety is also referred to as a carboxyl group. When X is oxygen and R is hydrogen, the formula represents a ‘carboxylic acid’. Where X is oxygen and R′ is hydrogen, the formula represents a ‘formate’. Where X is oxygen and R or R′ is not hydrogen, the formula represents an “ester”. In general, where the oxygen atom of the above formula is replaced by a sulfur atom, the formula represents a ‘thiocarbonyl’ group. Where X is sulfur and R or R′ is not hydrogen, the formula represents a ‘thioester.’ Where X is sulfur and R is hydrogen, the formula represents a ‘thiocarboxylic acid.’ Where X is sulfur and R′ is hydrogen, the formula represents a ‘thioformate.’ Where X is a bond and R is not hydrogen, the above formula represents a ‘ketone.’ Where X is a bond and R is hydrogen, the above formula represents an ‘aldehyde.’ 
     The term “substituted carbonyl” refers to a carbonyl, as defined above, wherein one or more hydrogen atoms in R, R′ or a group to which the moiety 
     
       
         
         
             
             
         
       
     
     is attached, are independently substituted. Such substituents include, but are not limited to, halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (such as a carboxyl, alkoxycarbonyl, formyl, or an acyl), silyl, ether, ester, thiocarbonyl (such as a thioester, a thioacetate, or a thioformate), alkoxyl, phosphoryl, phosphate, phosphonate, phosphinate, amino (or quarternized amino), amido, amidine, imine, cyano, nitro, azido, sulfhydryl, alkylthio, sulfate, sulfonate, sulfamoyl, sulfonamido, sulfonyl, heterocyclyl, alkylaryl, haloalkyl, —CN, aryl, heteroaryl, and combinations thereof. 
     The term “carboxyl” is as defined above for the formula 
     
       
         
         
             
             
         
       
     
     and is defined more specifically by the formula —R iv COOH, wherein R iv  is an alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, alkylaryl, arylalkyl, aryl, or heteroaryl. In preferred forms, a straight chain or branched chain alkyl, alkenyl, and alkynyl have 30 or fewer carbon atoms in its backbone (e.g., C 1 -C 30  for straight chain alkyl, C 3 -C 30  for branched chain alkyl, C 2 -C 30  for straight chain alkenyl and alkynyl, C 3 -C 30  for branched chain alkenyl and alkynyl), preferably 20 or fewer, more preferably 15 or fewer, most preferably 10 or fewer. 
     Likewise, preferred cycloalkyls, heterocyclyls, aryls and heteroaryls have from 3-10 carbon atoms in their ring structure, and more preferably have 5, 6 or 7 carbons in the ring structure. 
     The term “substituted carboxyl” refers to a carboxyl, as defined above, wherein one or more hydrogen atoms in R iv  are substituted. Such substituents include, but are not limited to, halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (such as a carboxyl, alkoxycarbonyl, formyl, or an acyl), silyl, ether, ester, thiocarbonyl (such as a thioester, a thioacetate, or a thioformate), alkoxyl, phosphoryl, phosphate, phosphonate, phosphinate, amino (or quarternized amino), amido, amidine, imine, cyano, nitro, azido, sulfhydryl, alkylthio, sulfate, sulfonate, sulfamoyl, sulfonamido, sulfonyl, heterocyclyl, alkylaryl, haloalkyl, —CN, aryl, heteroaryl, and combinations thereof. 
     The term “phenoxy” is recognized, and refers to a compound of the formula —ORv wherein R v  is (i.e., —O—C 6 H 5 ). One of skill in the art recognizes that a phenoxy is a species of the aroxy genus. 
     The term “substituted phenoxy” refers to a phenoxy group, as defined above, having one or more substituents replacing one or more hydrogen atoms on one or more carbons of the phenyl ring. Such substituents include, but are not limited to, halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (such as a carboxyl, alkoxycarbonyl, formyl, or an acyl), silyl, ether, ester, thiocarbonyl (such as a thioester, a thioacetate, or a thioformate), alkoxyl, phosphoryl, phosphate, phosphonate, phosphinate, amino (or quarternized amino), amido, amidine, imine, cyano, nitro, azido, sulfhydryl, alkylthio, sulfate, sulfonate, sulfamoyl, sulfonamido, sulfonyl, heterocyclyl, alkylaryl, haloalkyl, —CN, aryl, heteroaryl, and combinations thereof. 
     The terms “aroxy” and “aryloxy,” as used interchangeably herein, are represented by —O-aryl or —O-heteroaryl, wherein aryl and heteroaryl are as defined herein. 
     The terms “substituted aroxy” and “substituted aryloxy,” as used interchangeably herein, represent −O-aryl or —O-heteroaryl, having one or more substituents replacing one or more hydrogen atoms on one or more ring atoms of the aryl and heteroaryl, as defined herein. Such substituents include, but are not limited to, halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (such as a carboxyl, alkoxycarbonyl, formyl, or an acyl), silyl, ether, ester, thiocarbonyl (such as a thioester, a thioacetate, or a thioformate), alkoxyl, phosphoryl, phosphate, phosphonate, phosphinate, amino (or quarternized amino), amido, amidine, imine, cyano, nitro, azido, sulfhydryl, alkylthio, sulfate, sulfonate, sulfamoyl, sulfonamido, sulfonyl, heterocyclyl, alkylaryl, haloalkyl, —CN, aryl, heteroaryl, and combinations thereof. 
     The term “alkylthio” refers to an alkyl group, as defined above, having a sulfur radical attached thereto. The “alkylthio” moiety is represented by —S-alkyl. Representative alkylthio groups include methylthio, ethylthio, and the like. The term “alkylthio” also encompasses cycloalkyl groups having a sulfur radical attached thereto. 
     The term “substituted alkylthio” refers to an alkylthio group having one or more substituents replacing one or more hydrogen atoms on one or more carbon atoms of the alkylthio backbone. Such substituents include, but are not limited to, halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (such as a carboxyl, alkoxycarbonyl, formyl, or an acyl), silyl, ether, ester, thiocarbonyl (such as a thioester, a thioacetate, or a thioformate), alkoxyl, phosphoryl, phosphate, phosphonate, phosphinate, amino (or quarternized amino), amido, amidine, imine, cyano, nitro, azido, sulfhydryl, alkylthio, sulfate, sulfonate, sulfamoyl, sulfonamido, sulfonyl, heterocyclyl, alkylaryl, haloalkyl, —CN, aryl, heteroaryl, and combinations thereof. 
     The term “phenylthio” is art recognized, and refers to —S—C 6 H 5 , i.e., a phenyl group attached to a sulfur atom. 
     The term “substituted phenylthio” refers to a phenylthio group, as defined above, having one or more substituents replacing a hydrogen on one or more carbons of the phenyl ring. Such substituents include, but are not limited to, halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (such as a carboxyl, alkoxycarbonyl, formyl, or an acyl), silyl, ether, ester, thiocarbonyl (such as a thioester, a thioacetate, or a thioformate), alkoxyl, phosphoryl, phosphate, phosphonate, phosphinate, amino (or quarternized amino), amido, amidine, imine, cyano, nitro, azido, sulfhydryl, alkylthio, sulfate, sulfonate, sulfamoyl, sulfonamido, sulfonyl, heterocyclyl, alkylaryl, haloalkyl, —CN, aryl, heteroaryl, and combinations thereof. 
     “Arylthio” refers to —S-aryl or —S-heteroaryl groups, wherein aryl and heteroaryl as defined herein. 
     The term “substituted arylthio” represents —S-aryl or —S-heteroaryl, having one or more substituents replacing a hydrogen atom on one or more ring atoms of the aryl and heteroaryl rings as defined herein. Such substituents include, but are not limited to, halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (such as a carboxyl, alkoxycarbonyl, formyl, or an acyl), silyl, ether, ester, thiocarbonyl (such as a thioester, a thioacetate, or a thioformate), alkoxyl, phosphoryl, phosphate, phosphonate, phosphinate, amino (or quarternized amino), amido, amidine, imine, cyano, nitro, azido, sulfhydryl, alkylthio, sulfate, sulfonate, sulfamoyl, sulfonamido, sulfonyl, heterocyclyl, alkylaryl, haloalkyl, —CN, aryl, heteroaryl, and combinations thereof. 
     The terms “amide” or “amido” are used interchangeably, refer to both “unsubstituted amido” and “substituted amido” and are represented by the general formula: 
     
       
         
         
             
             
         
       
     
     wherein, E is absent, or E is 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 heterocyclyl, wherein independently of E, R and R′ each independently represent a hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted carbonyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted arylalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl, —(CH 2 ) m —R′″, or R and R′ taken together with the N atom to which they are attached complete a heterocycle having from 3 to 14 atoms in the ring structure; R′″ represents a hydroxy group, substituted or unsubstituted carbonyl group, an aryl, a cycloalkyl ring, a cycloalkenyl ring, a heterocycle, or a polycycle; and m is zero or an integer ranging from 1 to 8. In preferred forms, only one of R and R′ can be a carbonyl, e.g., R and R′ together with the nitrogen do not form an imide. In preferred forms, R and R′ each independently represent a hydrogen atom, substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, or —(CH 2 ) m —R′″. When E is oxygen, a carbamate is formed. The carbamate cannot be attached to another chemical species, such as to form an oxygen-oxygen bond, or other unstable bonds, as understood by one of ordinary skill in the art. 
     The term “sulfonyl” is represented by the formula 
     
       
         
         
             
             
         
       
     
     wherein E is absent, or E is alkyl, alkenyl, alkynyl, aralkyl, alkylaryl, cycloalkyl, aryl, heteroaryl, heterocyclyl, wherein independently of E, R represents a hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted amine, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted arylalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl, —(CH 2 ) m —R′″, or E and R taken together with the S atom to which they are attached complete a heterocycle having from 3 to 14 atoms in the ring structure; R′″ represents a hydroxy group, substituted or unsubstituted carbonyl group, an aryl, a cycloalkyl ring, a cycloalkenyl ring, a heterocycle, or a polycycle; and m is zero or an integer ranging from 1 to 8. In preferred forms, only one of E and R can be substituted or unsubstituted amine, to form a “sulfonamide” or “sulfonamido.” The substituted or unsubstituted amine is as defined above. 
     The term “substituted sulfonyl” represents a sulfonyl in which E, R, or both, are independently substituted. Such substituents include, but are not limited to, halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (such as a carboxyl, alkoxycarbonyl, formyl, or an acyl), silyl, ether, ester, thiocarbonyl (such as a thioester, a thioacetate, or a thioformate), alkoxyl, phosphoryl, phosphate, phosphonate, phosphinate, amino (or quarternized amino), amido, amidine, imine, cyano, nitro, azido, sulfhydryl, alkylthio, sulfate, sulfonate, sulfamoyl, sulfonamido, sulfonyl, heterocyclyl, alkylaryl, haloalkyl, —CN, aryl, heteroaryl, and combinations thereof. 
     The term “sulfonic acid” refers to a sulfonyl, as defined above, wherein R is hydroxyl, and E is absent, or E is substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted arylalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl. 
     The term “sulfate” refers to a sulfonyl, as defined above, wherein E is absent, oxygen, alkoxy, aroxy, substituted alkoxy or substituted aroxy, as defined above, and R is independently hydroxyl, alkoxy, aroxy, substituted alkoxy or substituted aroxy, as defined above. When E is oxygen, the sulfate cannot be attached to another chemical species, such as to form an oxygen-oxygen bond, or other unstable bonds, as understood by one of ordinary skill in the art. 
     The term “sulfonate” refers to a sulfonyl, as defined above, wherein E is oxygen, alkoxy, aroxy, substituted alkoxy or substituted aroxy, as defined above, and R is independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted amine, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted arylalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl, —(CH 2 ) m —R′″, R′″ represents a hydroxy group, substituted or unsubstituted carbonyl group, an aryl, a cycloalkyl ring, a cycloalkenyl ring, a heterocycle, or a polycycle; and m is zero or an integer ranging from 1 to 8. When E is oxygen, sulfonate cannot be attached to another chemical species, such as to form an oxygen-oxygen bond, or other unstable bonds, as understood by one of ordinary skill in the art. 
     The term “sulfamoyl” refers to a sulfonamide or sulfonamide represented by the formula 
     
       
         
         
             
             
         
       
     
     wherein E is absent, or E is 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 heterocyclyl, wherein independently of E, R and R′ each independently represent a hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted carbonyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted arylalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl, —(CH 2 ) m —R′″, or R and R′ taken together with the N atom to which they are attached complete a heterocycle having from 3 to 14 atoms in the ring structure; R′″ represents a hydroxy group, substituted or unsubstituted carbonyl group, an aryl, a cycloalkyl ring, a cycloalkenyl ring, a heterocycle, or a polycycle; and m is zero or an integer ranging from 1 to 8. In preferred forms, only one of R and R′ can be a carbonyl, e.g., R and R′ together with the nitrogen do not form an imide. 
     The term “phosphonyl” is represented by the formula 
     
       
         
         
             
             
         
       
     
     wherein E is absent, or E is 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 heterocyclyl, wherein, independently of E, Rv iv  and R vii  are independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted carbonyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted arylalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl, —(CH 2 ) m —R′″, or R and R′ taken together with the P atom to which they are attached complete a heterocycle having from 3 to 14 atoms in the ring structure; R′″ represents a hydroxy group, substituted or unsubstituted carbonyl group, an aryl, a cycloalkyl ring, a cycloalkenyl ring, a heterocycle, or a polycycle; and m is zero or an integer ranging from 1 to 8. 
     The term “substituted phosphonyl” represents a phosphonyl in which E, R vi  and R vii  are independently substituted. Such substituents include, but are not limited to, halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (such as a carboxyl, alkoxycarbonyl, formyl, or an acyl), silyl, ether, ester, thiocarbonyl (such as a thioester, a thioacetate, or a thioformate), alkoxyl, phosphoryl, phosphate, phosphonate, phosphinate, amino (or quarternized amino), amido, amidine, imine, cyano, nitro, azido, sulfhydryl, alkylthio, sulfate, sulfonate, sulfamoyl, sulfonamido, sulfonyl, heterocyclyl, alkylaryl, haloalkyl, —CN, aryl, heteroaryl, and combinations thereof. 
     The term “phosphoryl” defines a phosphonyl in which E is absent, oxygen, alkoxy, aroxy, substituted alkoxy or substituted aroxy, as defined above, and independently of E, R vi  and R vii  are independently hydroxyl, alkoxy, aroxy, substituted alkoxy or substituted aroxy, as defined above. When E is oxygen, the phosphoryl cannot be attached to another chemical species, such as to form an oxygen-oxygen bond, or other unstable bonds, as understood by one of ordinary skill in the art. When E, R vi  and R vii  are substituted, the substituents include, but are not limited to, halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (such as a carboxyl, alkoxycarbonyl, formyl, or an acyl), silyl, ether, ester, thiocarbonyl (such as a thioester, a thioacetate, or a thioformate), alkoxyl, phosphoryl, phosphate, phosphonate, phosphinate, amino (or quarternized amino), amido, amidine, imine, cyano, nitro, azido, sulfhydryl, alkylthio, sulfate, sulfonate, sulfamoyl, sulfonamido, sulfonyl, heterocyclyl, alkylaryl, haloalkyl, —CN, aryl, heteroaryl, and combinations thereof. 
     The term “polyaryl” refers to a chemical moiety that includes two or more aryls, heteroaryls, and combinations thereof. The aryls, heteroaryls, and combinations thereof, are fused, or linked via a single bond, ether, ester, carbonyl, amide, sulfonyl, sulfonamide, alkyl, azo, and combinations thereof. When two or more heteroaryls are involved, the chemical moiety can be referred to as a “polyheteroaryl.” 
     The term “substituted polyaryl” refers to a polyaryl in which one or more of the aryls, heteroaryls are substituted, with one or more substituents including, but not limited to, halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (such as a carboxyl, alkoxycarbonyl, formyl, or an acyl), silyl, ether, ester, thiocarbonyl (such as a thioester, a thioacetate, or a thioformate), alkoxyl, phosphoryl, phosphate, phosphonate, phosphinate, amino (or quarternized amino), amido, amidine, imine, cyano, nitro, azido, sulfhydryl, alkylthio, sulfate, sulfonate, sulfamoyl, sulfonamido, sulfonyl, heterocyclyl, alkylaryl, haloalkyl, —CN, aryl, heteroaryl, and combinations thereof. When two or more heteroaryls are involved, the chemical moiety can be referred to as a “substituted polyheteroaryl.” 
     The term “cyclic” refers to a substituted or unsubstituted cycloalkyl, substituted or unsubstituted cycloalkenyl, substituted or unsubstituted cycloalkynyl, substituted or unsubstituted heterocyclyl that, preferably, have from 3 to 20 carbon atoms, as geometric constraints permit. The cyclic structures are formed from single or fused ring systems. The substituted cycloalkyls, cycloalkenyls, cycloalkynyls and heterocyclyls are substituted as defined above for the alkyls, alkenyls, alkynyls and heterocyclyls, respectively. 
     II. Compositions 
     Described are two-coordinated d10 metal carbene complexes containing an imidazopyrazine ligand (e.g., pyrazine-fused N-heterocyclic carbene (NHC) ligand), an imidazopyridine ligand (e.g. pyridine-fused NHC), or a pyrrolopyrazine (e.g. pyrazine-fused NHC) ligand. The radiative properties of the compounds can be controlled by TADF. Preferably, the d10 metal carbene complexes contain a d10 metal in the +1-oxidation state (such as Cu(I), Ag(I), or Au(I)), a pyrazine-fused NHC ligand, and a carbazole ligand. A preferred pyrazine-fused NHC ligand or pyridine-fused N-heterocyclic carbene ligand contains a 2,6-diisopropylphenyl group covalently bonded to the nitrogen atoms of the imidazole moiety of the pyrazine-fused NHC ligand. The described compounds (i) are easy to produce in large scale, (ii) can be cheaper to produce because of the earth-abundant metal (copper), (iii) show tunable color emission properties, such as from blue-green to orange-red, (iv) are sublimable and solution-processable for OLED fabrication, (v) show improved OLED brightness and efficiency compared to existing emitters, and/or (vi) show improved device stability compared to reported d10 Cu/Ag/Au emitters. 
     The disclosed compounds have a structure: 
     
       
         
         
             
             
         
       
     
     wherein: 
     the compound has an overall neutral, negative, or positive charge, 
     M is copper, silver, or gold with an oxidation state of 0, +1, +2, or +3, preferably +1, 
     P′ has the structure: 
     
       
         
         
             
             
         
       
     
     D is carbon, 
     T, J, and W are independently carbon or nitrogen, wherein at least one of T, J, and W is nitrogen, wherein when T is carbon, J is nitrogen, or when T is nitrogen, J is carbon, and T, J, and W are bonded to one or no hydrogen atom according to valency, 
     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 one or no hydrogen atom according to valency, 
     R 1  and R 2  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 aroxy, substituted aroxy, 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 C 3 -C 20  cycloalkyl, unsubstituted C 3 -C 20  cycloalkyl, substituted C 2 -C 20  heterocyclyl, unsubstituted C 2 -C 20  heterocyclyl, substituted C 3 -C 20  cycloalkenyl, unsubstituted C 3 -C 20  cycloalkenyl, substituted C 3 -C 20  cycloalkynyl, or unsubstituted C 3 -C 20  cycloalkynyl, or R 1 , J, D, and R 2  together form an unsubstituted aryl, substituted aryl, unsubstituted heteroaryl, or substituted heteroaryl, 
     R 3  and R 4  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 aroxy, substituted aroxy, 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 C 3 -C 20  cycloalkyl, unsubstituted C 3 -C 20  cycloalkyl, substituted C 2 -C 20  heterocyclyl, unsubstituted C 2 -C 20  heterocyclyl, substituted C 3 -C 20  cycloalkenyl, unsubstituted C 3 -C 20  cycloalkenyl, substituted C 3 -C 20  cycloalkynyl, or unsubstituted C 3 -C 20  cycloalkynyl, 
     R 3 ′ and R 4 ′ are independently absent, 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 aroxy, substituted aroxy, 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 C 3 -C 20  cycloalkyl, unsubstituted C 3 -C 20  cycloalkyl, substituted C 2 -C 20  heterocyclyl, unsubstituted C 2 -C 20  heterocyclyl, substituted C 3 -C 20  cycloalkenyl, unsubstituted C 3 -C 20  cycloalkenyl, substituted C 3 -C 20  cycloalkynyl, or unsubstituted C 3 -C 20  cycloalkynyl, and 
     Z is substituted heteroaryl, unsubstituted heteroaryl, substituted polyheteroaryl, unsubstituted polyheteroaryl, substituted polyheterocyclyl, unsubstituted polyheterocyclyl, substituted heterocyclyl, or unsubstituted heterocyclyl, or —NR a R b , wherein R a  and R b  are independently hydrogen, substituted aryl, unsubstituted aryl, substituted heteroaryl, unsubstituted heteroaryl, substituted C 3 -C 20  cycloalkyl, unsubstituted C 3 -C 20  cycloalkyl, substituted heterocyclyl, unsubstituted heterocyclyl, substituted alkyl, or unsubstituted alkyl, 
     wherein (i) R 3  and R 4  are not both 3,5 dialkyl substituted aryl, (ii) R 3  and R 4  are not both 3,5 dialkyl substituted phenyl, (iii) R 3  and R 4  are not both 3,5 dimethylphenyl, (iv) R 3  and R 4  are not both 3,5 dimethylphenyl when M is Cu or Au, or (v) the compound is not 
     
       
         
         
             
             
         
       
     
     In some forms, the compound is as described above for Formula I, except that the compound has a structure: 
     
       
         
         
             
             
         
       
     
     wherein CY1 and CY2 are independently substituted aryl, unsubstituted aryl, substituted polyaryl, unsubstituted polyaryl, substituted heteroaryl, unsubstituted heteroaryl, substituted polyheteroaryl, unsubstituted polyheteroaryl, substituted C 3 -C 20  cycloalkyl, unsubstituted C 3 -C 20  cycloalkyl, substituted C 3 -C 20  cycloalkenyl, unsubstituted C 3 -C 20  cycloalkenyl, substituted C 3 -C 20  cycloalkynyl, or unsubstituted C 3 -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. 
     In some forms, the compound is a described above for Formula I or II, except that R 3 ′ and R 4 ′ are absent. 
     In some forms, the compound is as described above for Formula I or II, except that the compound has a structure: 
     
       
         
         
             
             
         
       
     
     wherein: 
     R 5  and R 6  are independently substituted alkyl or unsubstituted alkyl, and 
     n1 and n2 are independently integers between 0 and 5; between 1 and 5; between 2 and 5, such as 2; or between 3 and 5, such as 3. 
     In some forms, the compound is as described above for any of Formula I-III, except that the compound has a structure: 
     
       
         
         
             
             
         
       
     
     wherein: 
     n1 and n2 are independently integers between 1 and 5, between 2 and 5, or between 3 and 5, 
     L is absent, a single bond, substituted alkyl, —(CH 2 ) nx —, oxygen, sulfur, or NRx, wherein nx is an integer between 1 and 3 (such as 1, 2, or 3), and Rx is unsubstituted alkyl, substituted alkyl, unsubstituted aryl, or substituted aryl, and 
     CY3 and CY4 are independently unsubstituted aryl, substituted aryl, unsubstituted polyaryl, substituted polyaryl, unsubstituted heteroaryl, substituted heteroaryl, unsubstituted polyheteroaryl, substituted polyheteroaryl, unsubstituted C 3 -C 20  cycloalkyl, substituted C 3 -C 20  cycloalkyl, substituted C 3 -C 20  cycloalkenyl, unsubstituted C 3 -C 20  cycloalkenyl, substituted C 3 -C 20  cycloalkynyl, unsubstituted C 3 -C 20  cycloalkynyl, or a fused combination thereof. 
     In some forms, the compound is as described above for any of Formula I-IV, except that the compound has a structure: 
     
       
         
         
             
             
         
       
     
     wherein: 
     each Ra is independently hydrogen, unsubstituted alkyl, or substituted alkyl, 
     each Rb is independently unsubstituted alkyl, or substituted alkyl, L is absent, a single bond, substituted alkyl, —(CH 2 ) nx —, oxygen, sulfur, or NRx, wherein nx is an integer between 1 and 3 (such as 1, 2, or 3), and Rx is 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. 
     In some forms, the compound is as described above for any of Formula I-V, except that: 
     (i) T is nitrogen, J is carbon, and W is carbon, 
     (ii) T is nitrogen, J is carbon, and W is nitrogen, 
     (iii) T is carbon, J is nitrogen, and W is carbon, or 
     (iv) T is carbon, J is nitrogen, and W is nitrogen. 
     In some forms, the compound is as described above for Formula V, except that Ra is hydrogen, unsubstituted alkyl, or substituted alkyl, and Rb is unsubstituted alkyl or substituted alkyl. 
     In some forms, the compound is as described above for any of Formula I-V, except that P′ is selected from: 
     
       
         
         
             
             
         
       
     
     wherein: 
     Ra is hydrogen, unsubstituted alkyl, or substituted alkyl, and Rb is unsubstituted alkyl or substituted alkyl. 
     In some forms, the compound is as described above for any of Formula I-V, wherein when specified Ra is hydrogen, methyl, iso-propyl, or —CH(C 2 H 5 ) 2 , and Rb is methyl, iso-propyl, or —CH(C 2 H 5 ) 2 . 
     In some forms, the compound is as described above for Formula IV or V, except that CY3 and CY4 are independently unsubstituted aryl, substituted aryl, unsubstituted polyaryl, substituted polyaryl, unsubstituted heteroaryl, unsubstituted heteroaryl, or substituted C 3 -C 20  cycloalkenyl, unsubstituted C 3 -C 20  cycloalkenyl, or a fused combination thereof. In some forms, CY3 and CY4 are independently unsubstituted aryl, substituted aryl, unsubstituted heteroaryl, unsubstituted heteroaryl, substituted C 3 -C 20  cycloalkenyl, unsubstituted C 3 -C 20  cycloalkenyl, or a fused combination thereof. 
     In some forms, the compound is as described above for any of Formula I-V, except that Z has a structure: 
     
       
         
         
             
             
         
       
     
     wherein: 
     X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , X 7 , and X 8  are independently carbon or nitrogen, 
     Rx 1 , Rx 2 , Rx 3 , Rx 4 , Rx 5 , Rx 6 , Rx 7 , and Rx 8  are independently hydrogen, halogen, cyano, unsubstituted alkyl, substituted alkyl, unsubstituted alkoxy, substituted alkoxy, unsubstituted aryl, substituted aryl, unsubstituted heteroaryl, or substituted heteroaryl, wherein each Rx 1 , Rx 2 , Rx 3 , Rx 4 , Rx 5 , Rx 6 , Rx 7 , or Rx 8  is absent, when the corresponding X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , X 7 , or X 8  is nitrogen, or Rx 4  is a bond connected to a substituent on L, or adjacent Rxn groups together with the atoms in the ring to which they are bonded, together independently form five- or six-membered substituted aryl, unsubstituted aryl, substituted heteroaryl, unsubstituted heteroaryl, substituted C 3 -C 20  cycloalkenyl, unsubstituted C 3 -C 20  cycloalkenyl, or a fused combination thereof, wherein the n in the adjacent Rxn groups are sequential pairs of integers from 1 to 4, or 5 to 8, and 
     L is absent, a single bond, substituted alkyl, —(CH 2 ) nx —, oxygen, sulfur, or NRx, wherein nx is an integer between 1 and 3 (such as 1, 2, or 3), and Rx is unsubstituted alkyl, substituted alkyl, unsubstituted aryl, or substituted aryl. 
     In some forms, the compound is as described above for any of Formula I-V, except that Z has a structure: 
     
       
         
         
             
             
         
       
     
     wherein: 
     L′ is substituted aryl, unsubstituted aryl, substituted heteroaryl, or unsubstituted heteroaryl, preferably substituted aryl or unsubstituted aryl, preferably substituted phenyl or unsubstituted phenyl. 
     In some forms, the compound is as described above for any of Formula I-V, except that Z has a structure: 
     
       
         
         
             
             
         
       
     
     wherein: 
     X 1 , X 2 ,X 3 , X 4 , X 5 , X 6 , X 7 , and X 8  are independently carbon or nitrogen, and 
     Rx 1 , Rx 2 , Rx 3 , Rx 4 , Rx 5 , Rx 6 , Rx 7 , and Rx 8  are independently hydrogen, halogen, cyano, unsubstituted alkyl, substituted alkyl, unsubstituted alkoxy, substituted alkoxy, unsubstituted aryl, substituted aryl, unsubstituted heteroaryl, or substituted heteroaryl, wherein each Rx 1 , Rx 2 ,Rx 3 , Rx 4 , Rx 5 , Rx 6 , Rx 7 , or Rx 8  is absent, when the corresponding X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , X 7 , or X 8  is nitrogen, or adjacent Rxn groups together with the atoms in the ring to which they are bonded, together independently form five- or six-membered substituted aryl, unsubstituted aryl, substituted heteroaryl, unsubstituted heteroaryl, substituted C 3 -C 20  cycloalkenyl, unsubstituted C 3 -C 20  cycloalkenyl, or a fused combination thereof, wherein the n in the adjacent Rxn groups are sequential pairs of integers from 1 to 4, or 5 to 8. 
     In some forms, the compound is as described above for any of Formula I to V, wherein when specified Rx 1 , Rx 2 , Rx 3 , Rx 4 , Rx 5 , Rx 6 , Rx 7 , and Rx 8  are independently hydrogen, halogen, methyl, cyano, trifluoromethyl, tert-butyl, methoxy, phenyl, or pyridyl. 
     In some forms, the compound is as described above for any of Formula I-V, except that the compound has a structure: 
     
       
         
         
             
             
         
       
     
     preferably 
     
       
         
         
             
             
         
       
     
     wherein: 
     V″ is carbon, 
     U is carbon and V is nitrogen, or U is nitrogen and V is carbon, wherein U, V, and V″ are bonded to one or no hydrogen atom according to valency, 
     Ra is hydrogen, unsubstituted alkyl, or substituted alkyl, 
     R 7  and R 8  are independently absent, hydrogen, substituted alkyl, unsubstituted alkyl, cyano, halogen, hydroxyl, thiol, nitro-, unsubstituted alkoxy, substituted alkoxy, unsubstituted aroxy, substituted aroxy, substituted aryl, unsubstituted aryl, or adjacent R 7  groups or adjacent R 8  groups together with the atoms in the ring to which they are bonded, together independently form five- or six-membered substituted aryl, unsubstituted aryl, substituted heteroaryl, unsubstituted heteroaryl, substituted C 3 -C 20  cycloalkenyl, unsubstituted C 3 -C 20  cycloalkenyl, or a fused combination thereof, and 
     n3 and n4 are independently integers between 0 and 5, such as 0, 1, 2, 3, 4, 5. 
     In some forms, the compound is as described above for Formula VI, except that the compound has a structure: 
     
       
         
         
             
             
         
       
     
     preferably 
     
       
         
         
             
             
         
       
     
     wherein: 
     Rv is absent, hydrogen, substituted alkyl, or unsubstituted alkyl, and 
     R 7  and R 8  are independently hydrogen, substituted alkyl, unsubstituted alkyl, unsubstituted aryl, halogen, cyano, or Rv and R 7  together with the atoms in the rings to which they are bonded form five- or six-membered substituted aryl, unsubstituted aryl, substituted heteroaryl, unsubstituted heteroaryl, substituted C 3 -C 20  cycloalkenyl, unsubstituted C 3 -C 20  cycloalkenyl, or a fused combination thereof. 
     In some forms, the compound is as described above for Formula VI or VII, except that: 
     Rv is absent or hydrogen, R 7  and R 8  are independently hydrogen, iso-propyl, tert-butyl, phenyl, fluorine, or cyano, or 
     Rv and R 7  together form 
     
       
         
         
             
             
         
       
     
     In some forms, the compound is as described above for any of Formula I-VII, except that R 1  and R 2  are independently hydrogen, substituted alkyl, unsubstituted alkyl, substituted alkenyl, unsubstituted alkenyl, substituted alkynyl, unsubstituted alkynyl, substituted aryl, unsubstituted aryl, or R 1  and R 2  with the atoms in the ring to which they are bonded together form unsubstituted aryl, substituted aryl, unsubstituted heteroaryl, or substituted heteroaryl. In some forms, R 1  and R 2  are hydrogen. In some forms, R 1  and R 2  together form the structure: 
     
       
         
         
             
             
         
       
     
     In some forms, the compound is as described above for any of Formula I-VII, except that the compound has a structure: 
     
       
         
         
             
             
         
       
     
     preferably 
     
       
         
         
             
             
         
       
     
     wherein: 
     (i) M=Cu(I); W=N; Ra=H; U=CH; V=V″=carbon; Rv=H; R 7 =R 8 =H; 
     (ii) M=Cu(I); W=N; Ra=H; U=CH; V=V″=carbon; Rv=H; R 7 =H; R 8 =CN; 
     (iii) M=Cu(I); W=N; Ra=H; U=CH; V=V″=carbon; Rv=H; R 7 =R 8 =tert-butyl; 
     (iv) M=Cu(I); W=N; Ra=H; U=CH; V=V″=carbon; Rv=H; R 7 =R 8 =phenyl; 
     (v) M=Cu(I); W=N; Ra=H; U=CH; V=N; V″=carbon; Rv=absent; R 7 =R 8 =H; 
     (vi) M=Cu(I); W=U=CH; V=V″=carbon; Rv=H; Ra=iso-propyl; R 7 =R 8 =H; 
     (vii) M=Cu(I); W=N; Ra=H; U=CH; V=V″=carbon; R 8 =H; Rv and R 7  together form 
     
       
         
         
             
             
         
       
     
     (viii) M=Cu(I); W=U=CH; Ra=iso-propyl; V=V″=carbon; R 8 =H; Rv and R 7  together form 
     
       
         
         
             
             
         
       
     
     (ix) M=Cu(I); W=N; Ra=H; U=CH; V=V″=carbon; Rv=H; R 7 =R 8 =H; 
     (x) M=Cu(I); W=N; Ra=H; U=CH; V=V″=carbon; Rv=H; R 7 =H; R 8 =F; 
     (xi) M=Cu(I); W=N; Ra=H; U=CH; V=V″=carbon; Rv=H; R 7 =R 8 =methyl; 
     (xii) M=Au(I); W=N; Ra=H; U=CH; V=carbon; Rv=H; V″=carbon; R 7 =R 8 =H; 
     (xiii) M=Au(I); W=N; Ra=H; U=CH; V=carbon; Rv=H; V″=carbon; R 7 =H, R 8 =CN; 
     (xiv) M=Au(I); W=N; Ra=H; U=N; V=carbon; Rv=H; V″=carbon; R 7 =R 8 =H; 
     (xv) M=Au(I); W=U=CH; V=carbon; Rv=H; ; Ra=iso-propyl; V″=carbon; R 7 =R 8 =H; 
     (xvi) M=Au(I); W=N; Ra=H; U=CH; V=N; Rv=absent; V″=carbon; R 7 =R 8 =H; 
     (xvii) M=Au(I); W=N; Ra=H; U=CH; V=V″=carbon; Rv=H; R 7 =R 8 =CN; 
     (xviii) M=Au(I); W=N; Ra=hydrogen; U=CH; V=V″=carbon; R 8 =H; Rv and R 7  together form 
     
       
         
         
             
             
         
       
     
     (xix) M=Au(I); W=U=CH; Ra=iso-propyl; V=V″=carbon; Rv=H; R 7 =R 8 =tert-butyl; 
     (xx) M=Au(I); W=U=CH; Ra=iso-propyl; V=V″=carbon; Rv=H; R 7 =H; R 8 =F; 
     (xxi) M=Au(I); W=N; U=CH; Ra=H; V=V″=carbon; Rv=H; R 7 =R 8 =H; 
     (xxii) M=Au(I); W=N; U=CH; Ra=H; V=V″=carbon; Rv=H; R 7 =R 8 =tert-butyl; 
     (xxiii) M=Ag(I); W=N; U=CH; Ra=H; V=V″=carbon; Rv=H; R 7 =R 8 =H; 
     for (i), (ii), (iii), (iv), (v), (vi), (vii), (viii), (xii), (xiii), (xiv), (xv), (xvi), (xvii), (xviii), (xix), (xx), and (xxiii), the dashed lines denote the absence of bonds, and 
     for (ix), (x), (xi), (xxi), and (xxii), the dashed lines denote the presence of bonds. 
     In some forms, the compound has a structure selected from: 
     
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
     
     wherein M=Cu(I), Au(I), or Ag(I). 
     In some forms, the compound is as described above for any of Formula I-VII, except that substituted means substituted with one or more substituents selected from: halogen, hydroxyl, thiol, nitro-, unsubstituted alkyl, unsubstituted alkenyl, unsubstituted alkynyl, unsubstituted aryl, unsubstituted heteroaryl, unsubstituted arylalkyl, unsubstituted alkoxy, unsubstituted aroxy, unsubstituted alkylthio, unsubstituted arylthio, cyano, isocyano, unsubstituted carbonyl, unsubstituted carboxyl, oxo (═O), unsubstituted amino, unsubstituted amido, unsubstituted sulfonyl, unsubstituted sulfonic acid, unsubstituted phosphoryl, unsubstituted phosphonyl, unsubstituted polyaryl, or unsubstituted C 3 -C 20  cycloalkyl, and unsubstituted heterocyclyl. 
     In some forms, the compounds have a photoluminescence quantum yield (PLQY) between 0.50 and 0.95, such as between 0.58 and 0.92 in thin films. In some forms, the compounds have an emission decay lifetime (τ) between 0.20 μs and 0.45 μs, such as between 0.23 μs and 42 μs, in thin films. In some forms, the compounds have a PLQY between 0.50 and 0.95, such as between 0.58 and 0.92, and an emission decay lifetime (τ) between 0.20 μs and 0.45 μs, such as between 0.23 μs and 42 μs, in thin films. In some forms, the compounds have a radiative rate constant between 10-35×10 5  s −1 , such as between 15-21×10 5  s −1 , or ˜29×10 5  s −1 , in thin films. The films can 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(diphenylphosphoryl)dibenzo[b,d]furan (PPF), bis[2-(diphenylphosphino)phenyl]ether oxide (DPEPO), 3,3′-di(9H-carbazol-9-yl)-1,1′-biphenyl (mCBP), poly(methyl methacrylate) (PMMA), polystyrene (PS), or a combination thereof. 
     In some forms, the compounds act as sensitizers to transfer energy (such as exciton energy or photon energy) to a pure organic emitter. In some forms, the compounds act as sensitizers to transfer energy (such as exciton energy or photon energy) to a pure organic emitter that exhibits thermally activated delayed fluorescence. In some forms, the compounds act as sensitizers to transfer energy (such as exciton energy or photon energy) to a pure organic emitter that is boron-based. The phrase “pure organic emitter” as used throughout this application refers to a light-emitting organic molecule formed exclusively from main group elements of the periodic table, such that the light-emitting organic molecule does not contain a covalent bond or a dative bond to a main group metal. Notably, the phrase is not intended to define or specify a level of purity of a composition containing the light-emitting organic molecule. 
     Every compound within the above definition is intended to be and should be considered to be specifically disclosed herein. Further, every subgroup that can be identified within the above definition is intended to be and should be considered to be specifically disclosed herein. As a result, it is specifically contemplated that any compound or subgroup of compounds can be either specifically included for or excluded from use or included in or excluded from a list of compounds. For example, any one or more of the compounds described herein, with a structure depicted herein, or referred to in the Tables or the Examples herein can be specifically included, excluded, or combined in any combination, in a set or subgroup of such compounds. Such specific sets, subgroups, inclusions, and exclusions can be applied to any aspect of the compositions and methods described here. For example, a set of compounds that specifically excludes one or more particular compounds can be used or applied in the context of compounds per se (for example, a list or set of compounds), compositions including the compound (including, for example, pharmaceutical compositions), any one or more of the disclosed methods, or combinations of these. Different sets and subgroups of compounds with such specific inclusions and exclusions can be used or applied in the context of compounds per se, compositions including one or more of the compounds, or any of the disclosed methods. All of these different sets and subgroups of compounds—and the different sets of compounds, compositions, and methods using or applying the compounds—are specifically and individual contemplated and should be considered as specifically and individually described. 
     III. Methods of Making and Reagents Therefor 
     A. Compounds 
     The two-coordinated d10 metal carbene complexes and their ligands described herein can be synthesized using methods known in the art of organic chemical synthesis. The target compound can be synthesized by reacting the 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., a carbazole) over 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. B. Organic light-emitting devices 
     Also described are methods of making organic light-emitting devices, such as OLEDs, containing one or more d10 metal carbene complexes described above for any of Formula I-VIII. A preferred method of making the OLEDs involves vacuum deposition or solution processing techniques such as spin-coating and ink printing (such as, ink-jet printing or roll-to-roll printing). A method of making an OLED including a d10 metal carbene complex described herein is disclosed in the Examples. 
     IV. Methods of Using 
     Preferably, the d10 metal carbene complexes described herein are photo-stable, and are emissive at room temperatures, low temperatures, or a combination thereof. Accordingly, the compounds described herein can be incorporated into OLEDs, an organic photovoltaic cell (OPV), and organic field-effect transistor (OFET), or a light-emitting electrochemical cell (LEEC), and used in a stationary visual display unit, a mobile visual display unit, or an illumination device. Examples of units or devices include commercial applications such as smart phones, televisions, monitors, digital cameras, tablet computers, keyboards, clothes ornaments, garment accessories, wearable devices, medical monitoring devices, wall papers, advertisement panels, laptops, household appliances, office appliances, and lighting fixtures. Preferably, these units or devices are those that usually operate at room temperatures. 
     In some forms, the compounds can be included in a light-emitting layer. In some forms, one or more of the compounds can be included in a light-emitting layer containing a pure organic emitter, such that the one or more compounds act as a sensitizer to transfer energy (such as exciton energy or photon energy) to the pure organic emitter. In some forms, the one or more compounds have a higher-lying singlet state than the pure organic emitter. In some forms, the pure organic emitter exhibits thermally activated delayed fluorescence. In some forms, the pure organic emitter is boron-based. In some forms, the light-emitting layer can be included in an OLED. 
     The disclosed compounds, methods of using, and methods of making can be further understood through the following enumerated paragraphs or embodiments. 
     1. A compound having a structure: 
     
       
         
         
             
             
         
       
     
     wherein: 
     the compound has an overall neutral, negative, or positive charge, 
     M is copper, silver, or gold with an oxidation state of 0, +1, +2, or +3, preferably +1, 
     P′ has the structure: 
     
       
         
         
             
             
         
       
     
     D is carbon, 
     T, J, and W are independently carbon or nitrogen, wherein at least one of T, J, and W is nitrogen, wherein when T is carbon, J is nitrogen, or when T is nitrogen, J is carbon, and T, J, and W are bonded to one or no hydrogen atom according to valency, 
     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 one or no hydrogen atom according to valency, 
     R 1  and R 2  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 aroxy, substituted aroxy, 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 C 3 -C 20  cycloalkyl, unsubstituted C 3 -C 20  cycloalkyl, substituted C 2 -C 20  heterocyclyl, unsubstituted C 2 -C 20  heterocyclyl, substituted C 3 -C 20  cycloalkenyl, unsubstituted C 3 -C 20  cycloalkenyl, substituted C 3 -C 20  cycloalkynyl, or unsubstituted C 3 -C 20  cycloalkynyl, or R 1 , J, D, and R 2  together form an unsubstituted aryl, substituted aryl, unsubstituted heteroaryl, or substituted heteroaryl, 
     R 3  and R 4  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 aroxy, substituted aroxy, 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 C 3 -C 20  cycloalkyl, unsubstituted C 3 -C 20  cycloalkyl, substituted C 2 -C 20  heterocyclyl, unsubstituted C 2 -C 20  heterocyclyl, substituted C 3 -C 20  cycloalkenyl, unsubstituted C 3 -C 20  cycloalkenyl, substituted C 3 -C 20  cycloalkynyl, or unsubstituted C 3 -C 20  cycloalkynyl, R 3 ′ and R 4 ′ are independently absent, 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 aroxy, substituted aroxy, 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 C 3 -C 20  cycloalkyl, unsubstituted C 3 -C 20  cycloalkyl, substituted C 2 -C 20  heterocyclyl, unsubstituted C2 − C20 heterocyclyl, substituted C 3 -C 20  cycloalkenyl, unsubstituted C 3 -C 20  cycloalkenyl, substituted C 3 -C 20  cycloalkynyl, or unsubstituted C 3 -C 20  cycloalkynyl, and 
     Z is substituted heteroaryl, unsubstituted heteroaryl, substituted polyheteroaryl, unsubstituted polyheteroaryl, substituted polyheterocyclyl, unsubstituted polyheterocyclyl, substituted heterocyclyl, or unsubstituted heterocyclyl, or —NR a R b , wherein R a  and R b  are independently hydrogen, substituted aryl, unsubstituted aryl, substituted heteroaryl, unsubstituted heteroaryl, substituted C 3 -C 20  cycloalkyl, unsubstituted C 3 -C 20  cycloalkyl, substituted heterocyclyl, unsubstituted heterocyclyl, substituted alkyl, or unsubstituted alkyl, 
     wherein (i) R 3  and R 4  are not both 3,5 dialkyl substituted aryl, (ii) R 3  and R 4  are not both 3,5 dialkyl substituted phenyl, (iii) R 3  and R 4  are not both 3,5 dimethylphenyl, (iv) R 3  and R 4  are not both 3,5 dimethylphenyl when M is Cu or Au, or (v) the compound is not 
     
       
         
         
             
             
         
       
     
     2. The compound of paragraph 1, having a structure: 
     
       
         
         
             
             
         
       
     
     wherein CY1 and CY2 are independently substituted aryl, unsubstituted aryl, substituted polyaryl, unsubstituted polyaryl, substituted heteroaryl, unsubstituted heteroaryl, substituted polyheteroaryl, unsubstituted polyheteroaryl, substituted C 3 -C 20  cycloalkyl, unsubstituted C 3 -C 20  cycloalkyl, substituted C 3 -C 20  cycloalkenyl, unsubstituted C 3 -C 20  cycloalkenyl, substituted C 3 -C 20  cycloalkynyl, or unsubstituted C 3 -C 20  cycloalkynyl. 
     3. The compound of paragraph 1 or 2, wherein R 3 ′ and R 4 ′ are absent. 
     4. The compound of paragraph 2 or 3, wherein CY1 and CY2 are independently substituted aryl, unsubstituted aryl, substituted polyaryl, or unsubstituted polyaryl. 
     5. The compound of any one of paragraphs 2 to 4, wherein CY1 and CY2 are substituted aryl. 
     6. The compound of any one of paragraphs 1 to 5, having a structure: 
     
       
         
         
             
             
         
       
     
     wherein: 
     R 5  and R 6  are independently substituted alkyl or unsubstituted alkyl, and 
     n1 and n2 are independently integers between 0 and 5; between 1 and 5; between 3 and 5, such as 3; or between 2 and 5; such as 2. 
     7. The compound of any one of paragraphs 1 to 6, having a structure: 
     
       
         
         
             
             
         
       
     
     wherein: 
     n1 and n2 are independently integers between 1 and 5, between 2 and 5, or between 3 and 5, 
     L is absent, a single bond, substituted alkyl, —(CH 2 ) nx —, oxygen, sulfur, or NRx, wherein nx is an integer between 1 and 3 (such as 1, 2, or 3), and Rx is unsubstituted alkyl, substituted alkyl, unsubstituted aryl, or substituted aryl, and 
     CY3 and CY4 are independently unsubstituted aryl, substituted aryl, unsubstituted polyaryl, substituted polyaryl, unsubstituted heteroaryl, substituted heteroaryl, unsubstituted polyheteroaryl, substituted polyheteroaryl, unsubstituted C 3 -C 20  cycloalkyl, substituted C 3 -C 20  cycloalkyl, substituted C 3 -C 20  cycloalkenyl, unsubstituted C 3 -C 20  cycloalkenyl, substituted C 3 -C 20  cycloalkynyl, unsubstituted C 3 -C 20  cycloalkynyl, or a fused combination thereof. 
     8. The compound of any one of paragraphs 1 to 7, having a structure: 
     
       
         
         
             
             
         
       
     
     wherein: 
     each Ra is independently hydrogen, unsubstituted alkyl, or substituted alkyl, 
     each Rb is independently unsubstituted alkyl, or substituted alkyl, 
     L is absent, a single bond, substituted alkyl, —(CH 2 ) nx —, oxygen, sulfur, or NRx, wherein nx is an integer between 1 and 3 (such as 1, 2, or 3), and Rx is unsubstituted alkyl, substituted alkyl, unsubstituted aryl, or substituted aryl, and optionally wherein at least one of X and Y is nitrogen. 
     9. The compound of any one of paragraphs 1 to 8, wherein: 
     (i) T is nitrogen, J is carbon, and W is carbon, 
     (ii) T is nitrogen, J is carbon, and W is nitrogen, 
     (iii) T is carbon, J is nitrogen, and W is carbon, or 
     (iv) T is carbon, J is nitrogen, and W is nitrogen. 
     10. The compound of paragraph 8 or 9, wherein: 
     Ra is independently hydrogen, unsubstituted alkyl, or substituted alkyl, and 
     Rb is independently unsubstituted alkyl or substituted alkyl. 
     11. The compound of any one of paragraphs 1 to 10, wherein P′ is selected from: 
     
       
         
         
             
             
         
       
     
     wherein: 
     Ra is independently hydrogen, unsubstituted alkyl, or substituted alkyl, and 
     Rb is independently unsubstituted alkyl or substituted alkyl. 
     12. The compound of any one of paragraphs 8 to 11, wherein: 
     Ra is independently hydrogen, methyl, iso-propyl, or —CH(C2H5)2, and 
     Rb is independently methyl, iso-propyl, or —CH(C 2 H 5 ) 2 . 
     13. The compound of any one of paragraphs 7 to 12, wherein CY3 and CY4 are independently unsubstituted aryl, substituted aryl, unsubstituted polyaryl, substituted polyaryl, unsubstituted heteroaryl, unsubstituted heteroaryl, substituted C 3 -C 20  cycloalkenyl, unsubstituted C 3 -C 20  cycloalkenyl, or a fused combination thereof. 
     14. The compound of any one of paragraphs 7 to 13, wherein CY3 and CY4 are independently unsubstituted aryl, substituted aryl, unsubstituted heteroaryl, unsubstituted heteroaryl, substituted C 3 -C 20  cycloalkenyl, unsubstituted C 3 -C 20  cycloalkenyl, or a fused combination thereof. 
     15. The compound of any one of paragraphs 1 to 14, wherein Z has a structure: 
     
       
         
         
             
             
         
       
     
     wherein: 
     X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , X 7 , and X 8  are independently carbon or nitrogen, Rx 1 , Rx 2 ,Rx 3 , Rx 4 , Rxs, Rx 6 , Rx 7 , and Rx 8  are independently hydrogen, halogen, cyano, unsubstituted alkyl, substituted alkyl, unsubstituted alkoxy, substituted alkoxy, unsubstituted aryl, substituted aryl, unsubstituted heteroaryl, or substituted heteroaryl, wherein each Rx 1 , Rx 2 , Rx 3 , Rx 4 , Rxs, Rx 6 , Rx 7 , or Rx 8  is absent, when the corresponding X 1 , X 2 ,X 3 , X 4 , X 5 , X 6 , X 7 , or X 8  is nitrogen, or Rx 4  is a bond connected to a substituent on L, or adjacent Rxn groups together with the atoms in the ring to which they are bonded, together independently form five- or six-membered substituted aryl, unsubstituted aryl, substituted heteroaryl, unsubstituted heteroaryl, substituted C 3 -C 20  cycloalkenyl, unsubstituted C 3 -C 20  cycloalkenyl, or a fused combination thereof, wherein the n in the adjacent Rxn groups are sequential pairs of integers from 1 to 4, or 5 to 8, and 
     L is absent, a single bond, substituted alkyl, —(CH 2 ) nx —, oxygen, sulfur, or 
     NRx, wherein nx is an integer between 1 and 3 (such as 1, 2, or 3), and Rx is unsubstituted alkyl, substituted alkyl, unsubstituted aryl, or substituted aryl. 
     16. The compound of any one of paragraphs 1 to 15, wherein Z has a structure: 
     
       
         
         
             
             
         
       
     
     wherein: 
     L′ is substituted aryl, unsubstituted aryl, substituted heteroaryl, or unsubstituted heteroaryl, preferably substituted aryl or unsubstituted aryl, preferably substituted phenyl or unsubstituted phenyl. 
     17. The compound of paragraph 15, wherein Z has a structure: 
     
       
         
         
             
             
         
       
     
     18. The compound of paragraph 15 or 17, wherein Rx 1 , Rx 2 , Rx 3 , Rx 4 , Rx 5 , Rx 6 , Rx 7 , and Rx 8  are independently hydrogen, halogen, methyl, cyano, trifluoromethyl, tert-butyl, methoxy, phenyl, or pyridyl. 
     19. The compound of any one of paragraphs 1 to 18, wherein X and Y are nitrogen. 
     20. The compound of paragraph 1, having a structure: 
     
       
         
         
             
             
         
       
     
     preferably 
     
       
         
         
             
             
         
       
     
     wherein: 
     V″ is carbon, 
     U is carbon and V is nitrogen, or U is nitrogen and V is carbon, wherein U, V, and V″ are bonded to one or no hydrogen atom according to valency, 
     Ra is hydrogen, unsubstituted alkyl, or substituted alkyl, 
     R 7  and R 8  are independently absent, hydrogen, substituted alkyl, unsubstituted alkyl, cyano, halogen, hydroxyl, thiol, nitro-, unsubstituted alkoxy, substituted alkoxy, unsubstituted aroxy, substituted aroxy, substituted aryl, unsubstituted aryl, or adjacent R 7  groups or adjacent R 8  groups together with the atoms in the ring to which they are bonded, together independently form five- or six-membered substituted aryl, unsubstituted aryl, substituted heteroaryl, unsubstituted heteroaryl, substituted C 3 -C 20  cycloalkenyl, unsubstituted C 3 -C 20  cycloalkenyl, or a fused combination thereof, and 
     n3 and n4 are independently integers between 0 and 5, such as 0, 1, 2, 3, 4, 5. 
     21. The compound of paragraph 19, having a structure: 
     
       
         
         
             
             
         
       
     
     preferably 
     
       
         
         
             
             
         
       
     
     wherein: 
     Rv is absent, hydrogen, substituted alkyl, or unsubstituted alkyl, and 
     R 7  and R 8  are independently hydrogen, substituted alkyl, unsubstituted alkyl, unsubstituted aryl, halogen, or cyano, or 
     Rv and R 7  together with the atoms in the rings to which they are bonded form five- or six-membered substituted aryl, unsubstituted aryl, substituted heteroaryl, unsubstituted heteroaryl, substituted C 3 -C 20  cycloalkenyl, unsubstituted C 3 -C 20  cycloalkenyl, or a fused combination thereof. 
     22. The compound of paragraph 20 or 21, wherein: 
     Rv is absent or hydrogen, 
     R 7  and R 8  are independently hydrogen, iso-propyl, tert-butyl, phenyl, fluorine, or cyano, or 
     Rv and R 7  together form 
     
       
         
         
             
             
         
       
     
     23. The compound of any one of paragraphs 20 to 22, wherein: 
     R 1  and R 2  are independently hydrogen, substituted alkyl, unsubstituted alkyl, substituted alkenyl, unsubstituted alkenyl, substituted alkynyl, unsubstituted alkynyl, substituted aryl, unsubstituted aryl, or 
     R 1  and R 2  with the atoms in the ring to which they are bonded together form unsubstituted aryl, substituted aryl, unsubstituted heteroaryl, or substituted heteroaryl. 
     24. The compound of any one of paragraphs 20 to 23, wherein: 
     R 1  and R 2  are hydrogen, or 
     R 1  and R 2  together form the structure: 
     
       
         
         
             
             
         
       
     
     25. The compound of paragraph 24, having a structure: 
     
       
         
         
             
             
         
       
     
     preferably 
     
       
         
         
             
             
         
       
     
     wherein: 
     (i) M=Cu(I); W=N; Ra=H; U=CH; V=V″=carbon; Rv=H; R 7 =R 8 =H; 
     (ii) M=Cu(I); W=N; Ra=H; U=CH; V=V″=carbon; Rv=H; R 7 =H; R 8 =CN; 
     (iii) M=Cu(I); W=N; Ra=H; U=CH; V=V″=carbon; Rv=H; R 7 =R 8 =tert-butyl; 
     (iv) M=Cu(I); W=N; Ra=H; U=CH; V=V″=carbon; Rv=H; R 7 =R 8 =phenyl; 
     (v) M=Cu(I); W=N; Ra=H; U=CH; V=N; V″=carbon; Rv=absent; R 7 =R 8 =H; 
     (vi) M=Cu(I); W=U=CH; V=V″=carbon; Rv=H; Ra=iso-propyl; R 7 =R 8 =H; 
     (vii) M=Cu(I); W=N; Ra=H; U=CH; V=V″=carbon; R 8 =H; Rv and R 7  together form 
     
       
         
         
             
             
         
       
     
     (viii) M=Cu(I); W=U=CH; Ra=iso-propyl; V=V″=carbon; R 8 =H; Rv and R 7  together form 
     
       
         
         
             
             
         
       
     
     (ix) M=Cu(I); W=N; Ra=H; U=CH; V=V″=carbon; Rv=H; R 7 =R 8 =H; 
     (x) M=Cu(I); W=N; Ra=H; U=CH; V=V″=carbon; Rv=H; R 7 =H; R 8 =F; 
     (xi) M=Cu(I); W=N; Ra=H; U=CH; V=V″=carbon; Rv=H; R 7 =R 8 =methyl; 
     (xii) M=Au(I); W=N; Ra=H; U=CH; V=carbon; Rv=H; V″=carbon; R 7 =R 8 =H; 
     (xiii) M=Au(I); W=N; Ra=H; U=CH; V=carbon; Rv=H; V″=carbon; R 7 =H, R 8 =CN; 
     (xiv) M=Au(I); W=N; Ra=H; U=N; V=carbon; Rv=H; V″=carbon; R 7 =R 8 =H; 
     (xv) M=Au(I); W=U=CH; V=carbon; Rv=H; ; Ra=iso-propyl; V″ =carbon; R 7 =R 8 =H; 
     (xvi) M=Au(I); W=N; Ra=H; U=CH; V=N; Rv=absent; V″=carbon; R 7 =R 8 =H; 
     (xvii) M=Au(I); W=N; Ra=H; U=CH; V=V″=carbon; Rv=H; R 7 =R 8 =CN; 
     (xviii) M=Au(I); W=N; Ra=hydrogen; U=CH; V=V″=carbon; R 8 =H; Rv and R 7  together form 
     
       
         
         
             
             
         
       
     
     (xix) M=Au(I); W=U=CH; Ra=iso-propyl; V=V″=carbon; Rv=H; R 7 =R 8 =tert-butyl; 
     (xx) M=Au(I); W=U=CH; Ra=iso-propyl; V=V″=carbon; Rv=H; R 7 =H; R 8 =F; 
     (xxi) M=Au(I); W=N; U=CH; Ra=H; V=V″=carbon; Rv=H; R 7 =R 8 =H; 
     (xxii) M=Au(I); W=N; U=CH; Ra=H; V=V″=carbon; Rv=H; R 7 =R 8 =tert-butyl; 
     (xxiii) M=Ag(I); W=N; U=CH; Ra=H; V=V″=carbon; Rv=H; R 7 =R 8 =H; 
     for (i), (ii), (iii), (iv), (v), (vi), (vii), (viii), (xii), (xiii), (xiv), (xv), (xvi), (xvii), (xviii), (xix), (xx), and (xxiii), the dashed lines denote the absence of bonds, and 
     for (ix), (x), (xi), (xxi), and (xxii), the dashed lines denote the presence of bonds. 
     26. The compound of paragraph 1, having a structure: 
     
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
     
     wherein M=Cu(I), Au(I), or Ag(I). 
     27. The compound of any one of paragraphs 1 to 25, wherein substituted means substituted with one or more substituents selected from: halogen, hydroxyl, thiol, nitro-, unsubstituted alkyl, unsubstituted alkenyl, unsubstituted alkynyl, unsubstituted aryl, unsubstituted heteroaryl, unsubstituted arylalkyl, unsubstituted alkoxy, unsubstituted aroxy, unsubstituted alkylthio, unsubstituted arylthio, cyano, isocyano, unsubstituted carbonyl, unsubstituted carboxyl, oxo, unsubstituted amino, unsubstituted amido, unsubstituted sulfonyl, unsubstituted sulfonic acid, unsubstituted phosphoryl, unsubstituted phosphonyl, unsubstituted polyaryl, or unsubstituted C 3 -C 20  cycloalkyl, and unsubstituted heterocyclyl. 
     28. An organic electronic component containing the compound of any one of paragraphs 1 to 27. 
     29. The organic electronic component of paragraph 28, wherein the organic electronic component is an organic light-emitting diode (OLED) or a light-emitting electrochemical cell (LEEC). 
     30. The organic electronic component of paragraph 28 or 29, wherein the compounds are in a light-emitting layer. 
     31. The organic electronic component of any one of paragraphs 28 to 30, further containing an anode, a cathode, a hole transport region, and an electron transport region, 
     wherein the hole transport region contains a hole injection layer and/or a hole transport layer, and optionally an electron blocking layer, 
     wherein the electron transport region contains an electron transport layer and/or an electron injection layer, and optionally a hole blocking layer, 
     wherein the light emitting layer is located in between the anode and the cathode, 
     wherein the hole transport region is located between the anode and the light-emitting layer, and wherein the electron transport region is located in between the cathode and the light-emitting layer. 
     32. The organic electronic component of paragraph 29 or 30, wherein the light-emitting layer is fabricated by vacuum deposition, spin-coating or ink printing (such as, ink-jet printing or roll-to-roll printing). 
     33. A light-emitting layer containing the compound of any one of paragraphs 1 to 27. 
     34. A light-emitting layer comprising the compound of any one of paragraphs 1 to 27 and a pure organic emitter, wherein the compound acts as a sensitizer to transfer energy (such as exciton energy or photon energy) to the pure organic emitter. 
     35. A light-emitting layer comprising the compound of any one of claims  1  to  27  and a pure organic emitter, wherein the compound has a higher-lying singlet state than the pure organic emitter. 
     36. A light-emitting layer comprising the compound of any one of paragraphs 1 to 27 and a pure organic emitter, wherein the compound acts as a sensitizer to transfer energy (such as exciton energy or photon energy) to the pure organic emitter that exhibits thermally activated delayed fluorescence. 
     37. A light-emitting layer comprising the compound of any one of paragraphs 1 to 27 and a pure organic emitter, wherein the compound acts as a sensitizer to transfer energy (such as exciton energy or photon energy) to the pure organic emitter that is boron-based. 
     38. An OLED, containing the light-emitting layer of any one of paragraphs 33 to 37. 
     39. A device, containing the OLED of paragraph 38, wherein the device is selected from stationary visual display units, mobile visual display units, illumination units, keyboards, clothes, ornaments, garment accessories, wearable devices, medical monitoring devices, wall papers, tablet computers, laptops, advertisement panels, panel display units, household appliances, or office appliances. 
     EXAMPLES 
     Several d10 metal (Cu(I), Ag(I) or Au(I)) carbene complexes supported by pyrazine-fused N-heterocyclic carbene (NHC) ligand and carbazole derivatives have been prepared. These complexes show efficient TADF properties with high photoluminescence quantum yield (0.58-0.92) and short emission decay lifetime (0.23-0.42 μs) in a 1,3-bis(N-carbazolyl)benzene (mCP) thin film. The radiative decay rate constants of these complexes are impressively high, with k r  of 15-21×10 5  s −1  for Cu(I) complexes and k r  of ˜29×10 5  s −1  for Au(I) complexes. Both are higher than those of the previously reported Cu(I) (k r : 0.38-10×10 5  s −1 ) and Au(I) (0.53-22×10 5  s −1 ) counterparts supported by cyclic (alkyl)(amino)carbene (CAAC)(Nature Communications 2020, 11, 1758; Chem. Sci. 2020, 11, 435), monoamido-aminocarbene (MAC*)(J. Am. Chem. Soc. 2019, 141, 3576-3588) or diamidocarbene (DAC*)(J. Am. Chem. Soc. 2019, 141, 3576-3588). 
     It is believed that what the improved properties of the disclosed d10 metal carbene complexes are driven by the use of a pyrazine-fused NHC or a pyridine-fused NHC ligand decorated with bulky 2,6-diisopropylphenyl (DIPP) side groups in these two-coordinated d10 metal carbene complexes. The ligand structure increases the chemical and electrochemical stability, improves the electroluminescence performance as well as the photoluminescence quantum yield by suppressing the excited state structural distortions. The electroluminescence performance, i.e., ultra-high device brightness and remarkably long device lifetime, are unprecedented for d10 emitters. Further, the emission colors of this class of emitters are tunable by using carbazole derivatives with varying donor strength. For instance, green (Cu2 and Au2), yellow (Cu1, Au1, and Ag1), and red (Cu3) emitters have been prepared. 
     Example 1: Synthesis and characterization of compounds 
     Materials and Methods 
     The chemical reagents used for synthesis were purchased from commercial sources such as Dieckmann, Tiv Scientific, J &amp; K Scientific, BLDpharm, Bidepharm. They were directly used without further processing. 
     The solvents used for synthesis were purchased from Duksan, RCI Labscan, Scharlau. They were directly used without further processing.
         (i) Synthesis of pyrazine fused N-heterocyclic carbene ligand or pyridine fused N-heterocyclic carbene ligand       

     
       
         
         
             
             
         
       
         
         
           
             (a) Synthesis of N,N′-bis(2,6-diisopropylphenyl)pyrazine-2,3-diamine 
           
         
       
    
     To a 1-M solution of lithium hexamethyldisilazide (LiHMDS) in THF (3.5 eq.) in a sealed tube was added 2,6-diisopropylaniline (3.0 eq.). The resulting mixture was stirred under argon for 30 min. Then, 2,3-dichloropyrazine (1.0 eq.) was added into the reaction mixture and heated at 80° C. overnight. After reaction, the solvent was evaporated to dryness and the residue was extracted with DCM, which was then purified by column chromatography.  1 H NMR (500 MHz, CDCl 3 ) δ/ppm 7.49 (s, 1H), 7.34-7.30 (m, 1H), 7.24 (d, J=7.6 Hz, 2H), 5.72 (s, 1H), 3.10 (dt, J=13.5, 6.7 Hz, 2H), 1.19 (d, J=6.7 Hz, 16H).  13 C NMR (100 MHz, CDCl 3 ) 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 N 4]   + , cal. m/z: 431.3169, found: 431.3168.
         (b) Synthesis of 1,3-bis(2,6-diisopropylphenyl)imidazo[4,5-b]pyrazin-3-ium chloride (Pzlm-Cl)       

     To a round bottom flask was added N,N′-bis(2,6-diisopropylphenyl)pyrazine-2,3-diamine (1.2 mmol) in triethyl orthoformate. The mixture was heated at 150° C. for 6 hours. Then the mixture was cooled down to room temperature and excess chlorotrimethylsilane was added. The resulting reaction mixture was heated at 70° C. overnight. After reaction, the precipitate was collected by filtration, washed with Et 2 O and dried under air to give an off-white solid.  1 H NMR (500 MHz, CDCl 3 ) δ/ppm 13.64 (br s, 1H), 8.87 (s, 2H), 7.66 (t, J=7.5 Hz, 2H), 7.42 (d, J=8.0 Hz, 4H), 2.99 (m, 4H), 1.30 — 1.12 (m, 24H).  13 C NMR (100 MHz, CDCl 3 ) 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 H 37 N 4 ] + , cal. m/z: 441.3013, found: 441.3013. 
     
       
         
         
             
             
         
       
       
         
         
             
             
         
       
         
         
           
             (c) Synthesis of 2-chloro-N-(2,4,6-triisopropylphenyl)pyridin-3-amine 
           
         
       
    
     A mixture of 2-chloropyridin-3-amine (1.28 g, 10 mmol), (diacetoxyiodo)benzene (15 mmol), and triisopropylbenzene (100 mmol) in 1,1,1,3,3,3-hexafluoro-2-propanpol (40 mL) was stirred at room temperature overnight. After reaction, solvent was evaporated and the residue was purified by column chromatography. Yield: 2.85 g, 86%.  1 H NMR (500 MHz, CDCl 3 ) δ/ppm 7.73 (d, J=4.2 Hz, 1H), 7.08 (s, 2H), 6.95 (dd, J=8.0, 4.6 Hz, 1H), 6.45 (d, J=7.9 Hz, 1H), 5.63 (s, 1H), 3.02 (dt, J=13.7, 6.9 Hz, 2H), 2.93 (dt, J=13.8, 6.9 Hz, 1H), 1.29 (d, J=6.9 Hz, 6H), 1.18 (s, 6H), 1.10 (d, J=6.8 Hz, 6H).  13 C NMR (101 MHz, CDCl 3 ) 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 N 2 Cl] + , cal. m/z: 331.1936, found: 331.1933.
         (d) Synthesis of N 2 -(2,6-diisopropylphenyl)-N 3 -(2,4,6-triisopropylphenyl)-pyridine-2,3-diamine       

     To a solution of P T Bu 3  (100 mg, 0.50 mmol) in toluene (20 mL) was added Pd 2 (dba) 3  (100 mg, 0.11 mmol). 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)pyridin-3-amine (330 mg, 1.0 eq.) and NaO t Bu (289 mg, 3.0 eq.) were added into the solution in one port. The resulting suspension was heated at 130° C. for two days. After reaction, the solution was passed through a pad of celite and evaporated to dryness. The residue was purified by column chromatography on silica gel. Yield: 167 mg, 35%.  1 H NMR (500 MHz, CDCl 3 ) δ/ppm 7.69 (d, J=4.2 Hz, 1H), 7.36-7.31 (m, 1H), 7.29 (d, J=7.3 Hz, 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, 6.8 Hz, 2H), 3.13 (dt, J=13.6, 6.8 Hz, 2H), 2.98 (dt, J=13.8, 6.9 Hz, 1H), 1.26 (d, J=5.7 Hz, 24H), 1.20 (s, 6H).  13 C NMR (101 MHz, CDCl 3 ) 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 N 3]   + , cal. m/z: 472.3686, found: 472.3680.
         (e) Synthesis of 3-(2,6-diisopropylphenyl)-1-(2,4,6-triisopropylphenyl)-1H-imidazo [4,5-b]pyridin-3-ium tetrafluoroborate salt (PyIPr-BF 4 )       

     A solution of N 2 -(2,6-diisopropylphenyl)-N 3 -(2,4,6-triisopropylphenyl)-pyridin-2,3-amine (500 mg, 1.06 mmol) in triethyl orthoformate. Then, the mixture was heated at 150° C. for several hours. Then the mixture was cooled down to room temperature and excess chlorotrimethylsilane was added. The resulting reaction mixture was heated at 70° C. overnight. After reaction, solvent was evaporated and HBF 4  in methanol was added and stirred at room temperature for 30 min. After that, the solution was extracted with dichloromethane and saturated NaHCO 3  aqueous solution. The organic layer was dried over MgSO 4  and evaporated to give a white solid as 3-(2,6-diisopropylphenyl)-1-(2,4,6-triisopropylphenyl)-1H-imidazo[4,5-b]pyridin-3-ium tetrafluoroborate salt.  1 H NMR (500 MHz, CDCl 3 ) δ/ppm 10.32 (s, 1H), 8.85 (d, J=4.4 Hz, 1H), 7.90 (d, J=8.3 Hz, 1H), 7.76 (dd, J=8.2, 4.6 Hz, 1H), 7.66 (d, J=7.8 Hz, 2H), 7.45 (d, J=7.8 Hz, 3H), 7.27 (s, 2H), 3.04 (dt, J=13.6, 6.8 Hz, 2H), 2.22 (td, J=13.4, 6.6 Hz, 5H), 1.35 (d, J=6.8 Hz, 7H), 1.28 (dd, J=6.5, 2.9 Hz, 15H), 1.13 (t, J=6.2 Hz, 15H).  19 F NMR (471 MHz, CDCl 3 ) δ/ppm -151.89-151.94.  11 B NMR (160 MHz, CDCl 3 ) δ-1.31.  13 C NMR (126 MHz, CDCl 3 ) 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-BF 4 ] +  for [C 33 H 44 N 3 ] + , cal. m/z: 482.3529, found: 482.3516.
         (ii) Synthesis of metal-carbene complexes       

     
       
         
         
             
             
         
       
         
         
           
             (a) Synthesis of complex precursor PzImCuCl 
           
         
       
    
     To a solution of KO t Bu (1.2 eq.) in THF was added PzIm-Cl (1.0 eq.) and CuCl (1.2 eq.). The resulting mixture was stirred at room temperature under argon overnight. After reaction, the reaction mixture was passed through a layer of celite and then evaporated to dryness. The product was washed with EtOH and n-hexane.  1 H NMR (500 MHz, CDCl 3 ) δ/ppm  1 H NMR (500 MHz, CDCl 3 ) δ 8.52 (s, 2H), 7.62 (t, J=7.5 Hz, 2H), 7.42 (d, J=7.6 Hz, 4H), 2.38-2.27 (m, 4H), 1.30 (d, J=6.2 Hz, 12H), 1.12 (d, J=6.4 Hz, 12H).  13 C NMR (126 MHz, CDCl 3 ) δ/ppm 193.51, 146.31, 141.20, 140.18, 131.81, 130.38, 124.93, 29.63, 24.94, 23.84.
         (b) Synthesis of complex precursor PzImAuCl       

     To a suspension of PzIm-Cl (1.0 eq.) in THF was added KO t Bu (1.2 eq.) and the resulting mixture was stirred at room temperature under argon for 1 hour during which time a solution was formed that turned clear gradually. Then Au(tht)Cl (1.2 eq.) was added and the reaction mixture was left to be stirred in dark for 16 h. After reaction, the mixture was filtered through a pad of celite and then evaporated to dryness. The product was washed with EtOH and n-hexane. Yield: 185 mg, 27%.  1 H NMR (500 MHz, CDCl 3 ) δ/ppm 8.55 (s, 2H), 7.63 (t, J=7.8 Hz, 2H), 7.41 (d, J=7.8 Hz, 4H), 2.33 (dt, J=13.8, 6.9 Hz, 4H), 1.34 (d, J=6.9 Hz, 12H), 1.10 (t, J=7.9 Hz, 12H).  13 C NMR (126 MHz, CDCl 3 ) δ/ppm 188.22, 146.16, 141.49, 139.91, 131.70, 129.88, 124.75, 29.50, 24.40, 23.82.
         (c) Synthesis of complex precursor PzImAgCl       

     To a solution of PzIm-Cl (1.0 eq.) in DCM was added Ag 2 O (1.0 eq.). The resulting suspension was stirred in the dark at room temperature overnight. After reaction, the reaction mixture was filtered through a pad of celite then evaporated to dryness. The product was washed with EtOH and n-hexane.  1 H NMR (500 MHz, CDCl 3 ) δ/ppm 8.56 (s, 1H), 7.63 (t, J=7.7 Hz, 1H), 7.42 (d, J=7.8 Hz, 2H), 2.31 (dt, J=13.5, 6.8 Hz, 3H), 1.28 (d, J=6.8 Hz, 7H), 1.11 (d, J=6.7 Hz, 8H).  13 C NMR (126 MHz, CDCl 3 ) δ/ppm 146.32, 141.47, 140.12, 131.97, 130.65, 125.06, 29.60, 24.86, 23.96.
         (d) General procedure for the synthesis of complexes       

     To a solution of carbazole derivatives (1.5 eq.) in THF or a solution of pyrido[3,4-b]indole derivatives (1.5 eq.) in THF was added NaO t Bu (1.5 eq.), and the mixture was stirred for 30 min at room temperature under argon. Then the NHC-M-Cl (1.0 eq.) was added and the reaction mixture was stirred in the dark overnight. After reaction, the mixture was passed through a pad of celite. The filtrate was evaporated to dryness and the product was washed with n-hexane. 
     Cu1:  1 H NMR (500 MHz, CD 2 Cl 2 ) δ/ppm 8.59 (s, 2H), 7.85 (d, J=7.6 Hz, 4H), 7.59 (d, J=7.8 Hz, 2H), 6.96 (t, J=7.5 Hz, 2H), 6.85 (t, J=7.3 Hz, 2H), 6.23 (d, J=8.1 Hz, 2H), 2.54-2.45 (m, 4H), 1.26 (d, J=6.8 Hz, 12H), 1.18 (d, J=6.8 Hz, 12H).  13 C NMR (126 MHz, CD 2 Cl 2 ) 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. 
     Cu2:  1 H NMR (500 MHz, CD 2 Cl 2 ) δ/ppm 8.59 (s, 2H), 8.16 (s, 1H), 7.90-7.79 (m,3H), 7.58 (d, J=7.3 Hz, 4H), 7.17 (d, J=8.1 Hz, 1H), 7.05 (t, J=7.5 Hz, 1H), 6.95 (t, J=6.9 Hz, 1H), 6.27 (d, J=7.8 Hz, 1H), 6.12 (d, J=8.5 Hz, 1H), 2.46 (m, 4H), 1.22 (d, J=6.3 Hz, 12H), 1.16 (d, J=6.1 Hz, 12H).  13 C NMR (151 MHz, CD 2 Cl 2 ) 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. 
     Cu3:  1 H NMR (500 MHz, CD 2 Cl 2 ) δ/ppm 8.58 (s, 2H), 7.87-7.80 (m, 4H), 7.60 (d, J=7.8 Hz, 4H), 7.02 (d, J=8.5 Hz, 2H), 6.17 (d, J=8.5 Hz, 2H), 2.50 (dt, J=13.5, 6.7 Hz, 4H), 1.37 (s, 18H), 1.28 (d, J=6.8 Hz, 12H), 1.18 (d, J=6.7 Hz, 12H). 13 C NMR (126 MHz, CD 2 Cl 2 ) 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. 
     Cu4:  1 H NMR (500 MHz, CD 2 Cl 2 ) δ/ppm 8.61 (s, 2H), 8.18 (s, 2H), 7.87 (t, J=7.9 Hz, 2H), 7.68 (d, J=7.6 Hz, 4H), 7.62 (d, J=7.9 Hz, 4H), 7.42 (t, J=7.5 Hz, 4H), 7.30 (d, J=8.3 Hz, 2H), 7.25 (t, J=7.3 Hz, 2H), 6.30 (d, J=8.4 Hz, 2H), 2.52 (dq, J=13.8, 6.9 Hz, 4H), 1.30 (d, J=6.8 Hz, 12H), 1.20 (d, J=6.7 Hz, 12H). 13 C NMR (126 MHz, CD 2 Cl 2 ) δ/ppm 194.85, 150.39, 147.42, 143.41, 141.56, 140.68, 131.98, 131.34, 129.28, 128.96, 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 CuN 5 ] m/z cal. m/z: 821.35, found: 821.28. Anal. cal. for C53H52CuN 5 +H 2 O: C, 75.73; H, 6.48; N, 8.33; found: C, 75.71; H, 6.26; N, 8.10. 
     Cu5: 1 H NMR (500 MHz, CD 2 Cl 2 ) δ/ppm 8.64 (s, 2H), 8.03 (d, J=3.9 Hz, 1H), 7.96 (d, J=7.8 Hz, 1H), 7.89 (t, J=7.9 Hz, 2H), 7.77 (d, J=4.9 Hz, 1H), 7.70 (s, 1H), 7.63 (d, J=7.9 Hz, 4H), 7.12 (t, J=7.4 Hz, 1H), 6.96 (t, J=7.3 Hz, 1H), 6.30 (d, J=8.2 Hz, 1H), 2.52 (dt, J=13.7, 6.8 Hz, 4H), 1.29 (d, J=6.8 Hz, 12H), 1.21 (d, J=6.8 Hz, 12H). 
     Au1:  1 H NMR (400 MHz, CD 2 Cl 2 ) δ/ppm 8.58 (s, 2H), 7.87 (d, J=7.6 Hz, 2H), 7.79 (t, J=7.9 Hz, 2H), 7.54 (d, J=7.9 Hz, 4H), 7.08-6.99 (m, 2H), 6.91-6.82 (m, 2H), 6.61 (d, J=8.1 Hz, 2H), 2.48 (dt, J=13.7, 6.9 Hz, 4H), 1.32 (d, J=6.9 Hz, 12H), 1.14 (d, J=6.9 Hz, 12H).  13 C NMR (126 MHz, CD 2 Cl 2 ) δ/ppm 149.77, 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. 
     Au2:  1 H NMR (500 MHz, CD 2 Cl 2 ) δ/ppm 8.61 (s, 1H), 8.20 (s, OH), 7.91 (d, J=7.7 Hz, 1H), 7.80 (t, J=7.8 Hz, 1H), 7.55 (d, J=7.8 Hz, 2H), 7.26 (d, J=8.4 Hz, OH), 7.13 (t, J=7.6 Hz, 1H), 6.99 (t, J=7.4 Hz, 1H), 6.66 (d, J=8.2 Hz, 
     OH), 6.56 (d, J=8.4 Hz, 1H), 2.46 (dt, J=13.6, 6.8 Hz, 2H), 1.31 (d, J=6.8 Hz, 6H), 1.15 (d, J=6.8 Hz, 6H).  13 C NMR (126 MHz, CD 2 Cl 2 ) 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. 
     Au3: 1 H NMR (500 MHz, CD 2 Cl 2 ) δ/ppm 8.62 (s, 2H), 8.19 (dd, J=10.7, 5.9 Hz, 2H), 7.92 (d, J=7.8 Hz, 1H), 7.77 (t, J=7.8 Hz, 2H), 7.55 (d, J=7.8 Hz, 4H), 7.16-7.09 (m, 1H), 6.98 (t, J=7.4 Hz, 1H), 6.90-6.83 (m, 1H), 6.72 (d, J=8.1 Hz, 1H), 2.55 (dt, J=13.1, 6.6 Hz, 4H), 1.44 (d, J=6.8 Hz, 12H), 1.18 (d, J=6.8 Hz, 12H).  13 C NMR (126 MHz, CD 2 Cl 2 ) δ/ppm 191.17, 148.59, 146.78, 145.01, 141.46, 140.29, 131.44, 130.46, 126.52, 124.69, 124.43, 121.92, 119.80, 116.83, 116.13, 113.65, 112.28, 29.59, 23.98, 23.67. 
     Ag1:  1 H NMR (500 MHz, CD 2 Cl 2 ) δ/ppm 8.61 (s, 2H), 7.87 (d, J=7.5 Hz, 2H), 7.75 (t, J=7.7 Hz, 2H), 7.53 (d, J=7.7 Hz, 4H), 7.02 (t, J=7.4 Hz, 2H), 6.84 (t, J=7.2 Hz, 2H), 6.57 (d, J=8.0 Hz, 2H), 2.46 (dt, J=13.1, 6.5 Hz, 4H), 1.30 (d, J=6.6 Hz, 12H), 1.15 (d, J=6.6 Hz, 12H).  13 C NMR (126 MHz, CD 2 Cl 2 ) 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: the  13 C signal for carbenium carbon was not observed. 
     
       
         
         
             
             
         
       
         
         
           
             (e) General procedure for synthesis of complex precursor PyIPr-M-Cl 
           
         
       
    
     To a suspension of PyIPr-BF 4  (1.0 eq.) was added KHMDS (1.5 eq.) following by the addition of CuCl or Au(tht)Cl (1.5 eq.). The resulting mixture was stirred at room temperature under argon overnight. After reaction, the suspension was passed through a layer of celite and evaporated to dryness. The product was purified by recrystallization in DCM/EtOH. 
     PyIPrCuCl:  1 H NMR (500 MHz, CDCl 3 ) δ/ppm 8.52 (dd, J=4.7, 1.3 Hz, 1H), 7.58 (t, J=7.8 Hz, 1H), 7.49 (dd, J=8.1, 1.3 Hz, 1H), 7.40 (d, J=7.8 Hz, 2H), 7.35 (dd, J=8.2, 4.7 Hz, 1H), 7.21 (s, 2H), 3.03 (dt, J=13.8, 6.9 Hz, 1H), 2.36 (tt, J=13.6, 6.8 Hz, 4H), 1.36 (d, J=6.9 Hz, 6H), 1.29 (d, J=6.8 Hz, 12H), 1.11 (dd, J=6.7, 5.7 Hz, 12H).  13 C NMR (101 MHz, CDCl 3 ) 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 N 4 Cu] + , cal. m/z: 585.3013, found: 585.3026. 
     PyIPrAuCl:  1 H NMR (500 MHz, CDCl 3 ) δ/ppm 8.54-8.51 (m, 1H), 7.59 (t, J=7.8 Hz, 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, 6.9 Hz, 1H), 2.40-2.28 (m, 6H), 1.37 (d, J=6.9 Hz, 8H), 1.33 (d, J=6.9 Hz, 16H), 1.09 (t, J=6.4 Hz, 17H).  13 C NMR (101 MHz, CDCl 3 ) 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 N 4 Au] + , cal. m/z: 719.3388, found: 719.3378.
         (f) General procedure for the synthesis of complexes       

     To a solution of carbazole derivatives (1.5 eq.) in THF or a solution of pyrido[3,4-b]indole derivatives (1.5 eq.) in THF was added NaO t Bu (1.5 eq.), and the mixture was stirred for 30 min at room temperature under argon. Then PyIPr-M-Cl (1.0 eq.) was added and the reaction mixture was stirred in dark overnight. After reaction, the mixture was passed through a pad of celite. The filtrate was evaporated to dryness and the product was washed with n-hexane. 
     Cu6:  1 H NMR (500 MHz, acetone-d 6 ) 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 C NMR (126 MHz, acetone-d 6 ) 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. 
     Cu7:  1 H NMR (500 MHz, acetone-d 6 ) 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). 
     Cu8:  1 H NMR (500 MHz, acetone-d 6 ) 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). 
     Au4:  1 H NMR (500 MHz, CD 2 Cl 2 ) 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 C NMR (126 MHz, CD 2 Cl 2 ) 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. 
     Au5:  1 H NMR (500 MHz, acetone-d 6 ) δ/ppm 8.77 (s, 2H), 8.16 (s, 1H), 8.04 (d, J=5.1 Hz, 1H), 8.00 (d, J=7.8 Hz, 1H), 7.87 (t, J=7.9 Hz, 2H), 7.81 (d, J=5.0 Hz, 1H), 7.68 (d, J=7.9 Hz, 4H), 7.16 (t, J=7.6 Hz, 1H), 6.94 (t, J=7.2 Hz, 1H), 6.75 (d, J=8.3 Hz, 1H), 2.70 (dt, J=13.7, 6.8 Hz, 4H), 1.39 (d, J=6.9 Hz, 12H), 1.18 (d, J=6.8 Hz, 12H).  13 C NMR (126 MHz, acetone-d 6 ) 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. 
     Au6:  1 H NMR (500 MHz, acetone-d 6 ) δ/ppm 8.80 (s, 2H), 8.51 (s, 2H), 7.93 (t, J=7.8 Hz, 2H), 7.71 (d, J=7.9 Hz, 4H), 7.44 (d, J=8.5 Hz, 2H), 6.73 (d, J=8.5 Hz, 2H), 2.69 (dt, J=13.7, 6.9 Hz, 4H), 1.36 (d, J=6.8 Hz, 12H), 1.18 (d, J=6.8 Hz, 12H).  13 C NMR (126 MHz, CD 2 Cl 2 ) 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. 
     Au7:  1 H NMR (500 MHz, acetone-d 6 ) δ/ppm 8.75 (s, 2H), 8.28 (s, 1H), 7.95-7.80 (m, 3H), 7.85-7.69 (m, 5H), 7.42 (d, J=7.5 Hz, 1H), 7.24 (t, J=7.5 Hz, 1H), 7.14 (t, J=7.5 Hz, 1H), 6.98 (t, J=8.0 Hz, 1H), 6.85 (t, J=7.0 Hz, 1H), 6.65 (d, J=8.0 Hz, 1H), 2.74-2.65 (m, 4H), 1.44 (s, 6H), 1.40 (d, J=7.0 Hz, 12H), 1.18 (d, J=7.0 Hz, 12H). 
     Au8:  1 H NMR (500 MHz, acetone-d 6 ) δ/ppm 8.65 (dd, J=4.7, 1.2 Hz, 1H), 8.00 (dd, J=8.1, 1.2 Hz, 1H), 7.93 (d, J=1.8 Hz, 2H), 7.82 (t, J=7.8 Hz, 1H), 7.68 (dd, J=8.1, 4.8 Hz, 1H), 7.63 (d, J=7.9 Hz, 2H), 7.56 (s, 2H), 7.08 (dd, J=8.5, 2.0 Hz, 2H), 6.66 (d, J=8.5 Hz, 2H), 3.24 (dt, J=13.8, 6.9 Hz,1H), 2.63 (tt, J=13.7, 6.9 Hz, 4H), 1.50 (d, J=6.9 Hz, 6H), 1.38 (t, J=6.9 Hz, 12H), 1.35 (s, 18H), 1.21 (d, J=6.9 Hz, 6H), 1.17 (d, J=6.9 Hz, 6H).  13 C NMR (126 MHz, acetone-d 6 ) 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. 
     Au9:  1 H NMR (500 MHz, acetone-d 6 ) δ/ppm 8.66 (dd, J=4.7, 1.1 Hz, 1H), 8.02 (dd, J=8.1, 1.1 Hz, 1H), 7.91-7.81 (m, 2H), 7.70 (dd, J=8.2, 4.7 Hz, 1H), 7.64 (d, J=7.9 Hz, 2H), 7.61-7.53 (m, 3H), 7.02 (t, J=7.2 Hz, 1H), 6.83 (t, J=7.3 Hz, 1H), 6.81-6.76 (m, 1H), 6.73 (d, J=8.2 Hz, 1H), 6.61 (dd, J=8.8, 4.6 Hz, 1H), 3.23 (dq, J=14.0, 7.0 Hz, 1H), 2.62 (tt, J=13.6, 6.8 Hz, 4H), 1.49 (d, J=6.9 Hz, 6H), 1.36 (dd, J=11.9, 6.9 Hz, 12H), 1.19 (dd, J=20.0, 6.9 Hz, 12H).  19 F NMR (471 MHz, acetone-d 6 ) δ/ppm -129.97.  13 C NMR (126 MHz, acetone-d 6 ) 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. 
     
       
         
         
             
             
         
       
       
         
         
             
             
         
       
     
     Cu9:  1 H NMR (500 MHz, acetone-d 6 ) δ/ppm 8.23 (dd, J=6.5, 3.5 Hz, 2H), 8.00-7.96 (m, 2H), 7.95 (t, J=7.9 Hz, 2H), 7.82 (d, J=7.6 Hz, 2H), 7.74 (d, J=7.9 Hz, 4H), 6.96-6.90 (m, 2H), 6.83-6.77 (m, 2H), 6.28 (d, J=8.1 Hz, 2H), 2.86 (dt, J=13.7, 6.8 Hz, 4H), 1.30 (d, J=6.9 Hz, 12H), 1.19 (d, J=6.8 Hz, 12H). 
     Cu10:  1 H NMR (500 MHz, CD 2 Cl 2 ) δ/ppm 8.27 (dd, J=6.5, 3.5 Hz, 2H), 7.95-7.86 (m, 4H), 7.80 (d, J=7.6 Hz, 1H), 7.64 (d, J=7.9 Hz, 4H), 7.50 (dd, J=9.5, 2.5 Hz, 1H), 6.99 (t, J=7.1 Hz, 1H), 6.85 (t, J=7.3 Hz, 1H), 6.77-6.71 (m, 1H), 6.23 (d, J=8.1 Hz, 1H), 6.09 (dd, J=8.8, 4.5 Hz, 1H), 2.60 (dt, J=13.6, 6.7 Hz, 4H), 1.27 (d, J=6.9 Hz, 12H), 1.19 (d, J=6.8 Hz, 12H). 
     Cu11:  1 H NMR (500 MHz, CD 2 Cl 2 ) δ/ppm 8.26 (dd, J=6.4, 3.5 Hz, 2H), 7.93-7.85 (m, 4H), 7.68-7.59 (m, 4H), 6.79 (d, J=7.6 Hz, 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). 
     
       
         
         
             
             
         
       
       
         
         
             
             
         
       
     
     Au10:  1 H NMR (500 MHz, CD 2 Cl 2 ) δ/ppm 8.26 (dd, J=6.4, 3.5 Hz, 1H), 7.89 (ddd, J=20.1, 11.2, 5.6 Hz, 3H), 7.62 (d, J=7.9 Hz, 2H), 7.06 (t, J=7.4 Hz, 1H), 6.90 (t, J=7.3 Hz, 1H), 6.61 (d, J=8.1 Hz, 1H), 2.60 (dt, J=13.6, 6.8 Hz, 2H), 1.36 (d, J=6.8 Hz, 7H), 1.18 (d, J=6.8 Hz, 7H). 13 C NMR (126 MHz, CD 2 Cl 2 ) δ/ppm 198.43, 149.76, 147.78, 141.36, 140.88, 132.14, 131.37, 130.90, 129.76, 125.44, 124.37, 124.20, 119.75, 116.87, 113.97, 30.25, 24.61, 24.42. 
     Au11:  1 H NMR (400 MHz, CD 2 Cl 2 ) δ/ppm 8.26 (dd, J=6.5, 3.5 Hz, 2H), 7.94-7.83 (m, 6H), 7.62 (d, J=7.9 Hz, 4H), 7.12 (dd, J=8.5, 1.8 Hz, 2H), 6.53 (d, J=8.5 Hz, 2H), 2.60 (dt, J=13.7, 6.8 Hz, 4H), 1.38 (s, 18H), 1.37 (d, J=7.0 Hz, 12H), 1.18 (d, J=6.8 Hz, 12H). 13 C NMR (101 MHz, CD 2 Cl 2 ) 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. 
     The structures of Cu7-Cu11 and Au5-Aull are shown below: 
     
       
         
         
             
             
         
       
       
         
         
             
             
         
       
     
     Results 
     The results of the instant work are presented below. The photophysical properties of complexes can be evaluated by maximum emission wavelength (λ em ), emission lifetime (τ em ), emission quantum yield (Φ em ), radiative decay rate (k r ), and non-radiative decay rate (k nr ). The tem values of complexes in degassed toluene and MCP (1,3-bis(N-carbazolyl)benzene) thin films were directly obtained by absolute measurement using Hamamatsu C11347 Quantaurus-QY Absolute PL quantum yield spectrometer (PL stands for photoluminescence). Maximum emission wavelength λ em , are read from the emission spectra. The emission lifetime (τ em ) measurement was performed on a Quanta Ray GCR 150-10 pulsed Nd:YAG laser system (pulse output: 355 nm). The intensity of emission decay was monitored as a function of time. 
     
       
         
           
             
               I 
               ⁡ 
               ( 
               t 
               ) 
             
             = 
             
               
                 I 
                 0 
               
               ⁢ 
               
                 e 
                 
                   
                     - 
                     t 
                   
                   / 
                   τ 
                 
               
             
           
         
       
     
     I 0  is the initial emission intensity, I(t) is the emission intensity at time t, τ is the emission lifetime and t is the time. The emission lifetime was determined by fitting the exponential decay using Origin software. The k r  and k nr  of complex can be calculated using equations k r =Φ em  and k nr =(1-Φ em )/τ em , respectively.
         Photophysical characterization of the compounds       

     
       
         
           
               
             
               
                 TABLE 1 
               
             
            
               
                   
               
               
                 Summary of photophysical properties measured in different media 
               
            
           
           
               
               
               
               
               
               
            
               
                 Complex 
                 λ em /nm 
                 τ em /μs 
                 Φ em   
                 k r (×10 5 )/s −1   
                 k nr (×10 5 )/s −1   
               
               
                   
               
            
           
           
               
            
               
                 Degassed toluene at 298 K 
               
            
           
           
               
               
               
               
               
               
            
               
                 Cu1 
                 620 
                 0.18 
                 0.29 
                 16.1 
                 39.4 
               
               
                 Cu2 
                 555 
                 0.36 
                 0.58 
                 16.1 
                 11.6 
               
               
                 Cu3 
                 660 
                 0.11 a   
                 0.14 
                 12.7 
                 78.2 
               
               
                 Cu4 
                 635 
                 0.12 
                 0.15 
                 12.2 
                 70.8 
               
               
                 Cu6 
                 502 
                 0.55 
                 0.74 
                 13.5 
                 4.7 
               
               
                 Cu9 
                 721 
                 &lt;0.1 
                 0.13 
                 — 
                 — 
               
               
                 Au1 
                 620 
                 0.17 
                 0.17 
                 10.0 
                 8.3 
               
               
                 Au2 
                 550 
                 0.33 a   
                 0.73 
                 22.1 
                 8.2 
               
               
                 Au3 
                 553 
                 0.45 
                 0.53 
                 11.7 
                 10.4 
               
               
                 Au4 
                 500 
                 0.45 
                 0.76 
                 16.9 
                 5.3 
               
               
                 Au5 
                 570 
                 0.36 
                 0.60 
                 16.6 
                 11.1 
               
               
                 Au6 
                 485 
                 0.36 
                 0.72 
                 20.0 
                 7.8 
               
               
                 Au8 
                 526 
                 0.54 
                 0.75 
                 13.9 
                 4.6 
               
               
                 Au9 
                 500 
                 0.58 
                 0.82 
                 14.1 
                 3.1 
               
               
                 Ag1 
                 676 
                 &lt;0.1 
                 0.06 
                 — 
                 — 
               
            
           
           
               
            
               
                 2 wt/wt % in MCP film at 298 K 
               
            
           
           
               
               
               
               
               
               
            
               
                 Cu1 
                 576 
                 0.42 
                 0.80 
                 19.0 
                 4.8 
               
               
                 Cu2 
                 525 
                 0.41 
                 0.89 
                 21.7 
                 2.7 
               
               
                 Cu3 
                 610 
                 0.39 
                 0.58 
                 14.9 
                 10.8 
               
               
                 Cu4 
                 568 
                 0.36 
                 0.76 
                 21.1 
                 6.6 
               
               
                 Cu5 
                 525 
                 0.44 
                 0.40 
                  9.1 
                 13.6 
               
               
                 Cu9 
                 637 
                 0.35 
                 0.67 
                 19.1 
                 9.4 
               
               
                 Cu10 
                 630 
                 0.34 
                 0.61 
                 17.9 
                 11.5 
               
               
                 Cu11 
                 677 
                 0.27 
                 0.39 
                 14.4 
                 22.6 
               
               
                 Au1 
                 557 
                 0.33 
                 0.92 
                 27.9 
                 2.4 
               
               
                 Au2 
                 516 
                 0.27 
                 0.80 
                 29.6 
                 7.4 
               
               
                 Au3 
                 504 
                 0.47 
                 0.69 
                 14.6 
                 6.6 
               
               
                 Au10 
                 642 
                 0.32 
                 0.69 
                 21.6 
                 9.7 
               
               
                 Au11 
                 685 
                 0.27 
                 0.51 
                 18.8 
                 18.1 
               
               
                 Ag1 
                 565 
                 0.23 
                 0.72 
                 31.3 
                 12.2 
               
            
           
           
               
            
               
                 5 wt/wt % in MCP film at 298 K 
               
            
           
           
               
               
               
               
               
               
            
               
                 Cu6 
                 470 
                 0.47 
                 0.52 
                 11.1 
                 10.2 
               
               
                 Cu7 
                 592 
                 0.32 
                 0.76 
                 23.8 
                 7.5 
               
               
                 Cu8 
                 491 
                 0.77 a   
                 0.51 
                  6.6 
                 6.4 
               
               
                 Cu9 
                 651 
                 0.32 
                 0.57 
                 17.8 
                 13.4 
               
               
                 Cu10 
                 653 
                 0.27 
                 0.54 
                 20.0 
                 17.0 
               
               
                 Cu11 
                 709 
                 0.20 
                 0.29 
                 14.5 
                 35.5 
               
               
                 Au10 
                 658 
                 0.29 
                 0.73 
                 25.2 
                 9.3 
               
               
                 Au11 
                 706 
                 0.23 
                 0.41 
                 17.8 
                 25.7 
               
            
           
           
               
            
               
                 2 wt/wt % in PMMA film at 298 K 
               
            
           
           
               
               
               
               
               
               
            
               
                 Au4 
                 468 
                 0.75 a   
                 0.74 
                  9.9 
                 3.5 
               
               
                 Au5 
                 520 
                 0.56 
                 0.96 
                 17.1 
                 0.7 
               
               
                 Au6 
                 466 
                 0.70 a   
                 0.43 
                  6.1 
                 8.1 
               
               
                 Au7 
                 568 
                 0.24 
                 0.47 
                 19.6 
                 22.1 
               
               
                 Au8 
                 480 
                 0.64 
                 0.85 
                 13.3 
                 2.3 
               
               
                 Au9 
                 470 
                 1.23 a   
                 0.63 
                  5.1 
                 3.0 
               
            
           
           
               
            
               
                 2-MeTHF at 77 K 
               
            
           
           
               
               
               
               
               
               
            
               
                 Cu1 
                 500 
                 185 
                 — 
                 — 
                 — 
               
            
           
           
               
               
               
               
               
            
               
                 Cu2 
                 429 {398 (60%), 
                 — 
                 — 
                 — 
               
               
                   
                 2063 (40%)}, 
               
               
                   
                 455 (250) 
               
            
           
           
               
               
               
               
               
               
            
               
                 Cu3 
                 535 
                 104 
                 — 
                 — 
                 — 
               
               
                 Cu6 
                 429 
                 4000 
                 — 
                 — 
                 — 
               
               
                 Au1 
                 497 
                 78 
                 — 
                 — 
                 — 
               
            
           
           
               
               
               
               
               
            
               
                 Au2 
                 424 (162.4), 
                 — 
                 — 
                 — 
               
               
                   
                 450 (75.9) 
               
               
                 Au3 
                 428 (1122), 455 
                 — 
                 — 
                 — 
               
               
                   
                 {78 (95%), 
               
               
                   
                 984 (5%)} 
               
            
           
           
               
               
               
               
               
               
            
               
                 Au4 
                 424 
                 268 
                 — 
                 — 
                 — 
               
               
                 Au5 
                 473 
                 505 
                 — 
                 — 
                 — 
               
               
                 Au6 
                 418 
                 278 
                 — 
                 — 
                 — 
               
            
           
           
               
               
               
               
               
            
               
                 Au8 
                 427 (201), 436 (212), 
                 — 
                 — 
                 — 
               
               
                   
                 452 {62(58%), 
               
               
                   
                 280 (42%)} 
               
               
                 Au9 
                 441 (660); 
                 — 
                 — 
                 — 
               
               
                   
                 470 (730) 
               
            
           
           
               
               
               
               
               
               
            
               
                 Ag1 
                 504 
                 2.2 
                 — 
                 — 
                 — 
               
               
                   
               
               
                   a weighted average lifetime 
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 2 
               
             
            
               
                   
               
               
                 Device data for Cu1 
               
            
           
           
               
               
               
               
               
            
               
                   
                 CE [cd A −1 ] 
                 PE [lm W −1 ] 
                 EQE [%] 
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
            
               
                   
                 L max   
                   
                 at 1000 
                   
                 at 1000 
                   
                 at 1000 
                 CIE 
                 λ max   
               
               
                 Cu1 
                 [cd m −2 ] 
                 Max 
                 cd m −2   
                 Max 
                 cd m −2   
                 Max 
                 cd m −2   
                 (x, y) 
                 [nm] 
               
               
                   
               
               
                 2 wt/wt % 
                 153400 
                 60.00 
                 55.83 
                 62.83 
                 42.48 
                 20.00 
                 18.65 
                 (0.43, 0.55) 
                 556 
               
               
                 6 wt/wt % 
                 177400 
                 48.48 
                 45.75 
                 50.78 
                 31.94 
                 18.76 
                 17.72 
                 (0.49, 0.50) 
                 573 
               
               
                 8 wt/wt % 
                 222200 
                 44.69 
                 43.66 
                 46.20 
                 29.06 
                 18.72 
                 18.31 
                 (0.51, 0.48) 
                 582 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 3 
               
             
            
               
                   
               
               
                 Device lifetime measurement for Cu1. Device structure: ITO/HAT-CN 
               
               
                 (5 nm)/PT-301 (160 nm)/PT-603I (5 nm)/Cu1:LLP604 (20 nm)/PT74M 
               
               
                 (5 nm)/LET321:Liq (1:1, 25 nm)/Liq (1 nm)/Al (100 nm) 
               
            
           
           
               
               
               
               
               
               
            
               
                   
                 1 mA cm −2   
                 3 mA cm −2   
                 5 mA cm −2   
                   
                 LT@1000 cd m −2   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
            
               
                   
                 L 0   
                 LT50 
                 L 0   
                 LT50 
                 L 0   
                 LT50 
                   
                 LT90 
                 LT50 
               
               
                 Conc. 
                 [cd m −2 ] 
                 [h] 
                 [cd m −2 ] 
                 [h] 
                 [cd m −2 ] 
                 [h] 
                 n 
                 [h] 
                 [h] 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
            
               
                 2 wt/wt % 
                 5200 
                 396.6 
                 13000 
                 59 
                 20000 
                 28.02 
                 1.97 
                 362 
                 9233 
               
               
                 4 wt/wt % 
                 4300 
                 500 
                 11000 
                 79.3 
                 17000 
                 35.2 
                 1.94 
                 410 
                 8326 
               
               
                 6 wt/wt % 
                 4000 
                 1000 
                 10000 
                 82.7 
                 16000 
                 37.41 
                 2.01 
                 415 
                 8462 
               
               
                   
               
               
                 n denotes for acceleration factor in LT(L 1 ) = LT(L 0 ) × (L 0 /L 1 ) n   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 4 
               
             
            
               
                   
               
               
                 Device data for Cu2 
               
            
           
           
               
               
               
               
               
            
               
                   
                 CE [cd A −1 ] 
                 PE [lm W −1 ] 
                 EQE [%] 
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
            
               
                   
                 L 
                   
                 at 1000 
                   
                 at 1000 
                   
                 at 1000 
                 CIE 
                 λ max   
               
               
                 Cu2 
                 [cd m −2 ] 
                 Max 
                 cd m −2   
                 Max 
                 cd m −2   
                 Max 
                 cd m −2   
                 (x, y) 
                 [nm] 
               
               
                   
               
               
                 2 wt/wt % 
                 12100 
                 49.49 
                 41.55 
                 38.87 
                 23.69 
                 21.13 
                 17.68 
                 (0.19, 0.42) 
                 492 
               
               
                 4 wt/wt % 
                 14400 
                 53.37 
                 48.02 
                 39.72 
                 27.16 
                 20.76 
                 18.63 
                 (0.22, 0.46) 
                 495 
               
               
                 6 wt/wt % 
                 17300 
                 57.22 
                 49.96 
                 48.76 
                 26.20 
                 20.89 
                 18.22 
                 (0.25, 0.51) 
                 504 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 5a 
               
             
            
               
                   
               
               
                 Device lifetime measurement for Cu2. Device structure: ITO/HAT-CN 
               
               
                 (5 nm)/PT-301 (160 nm)/PT-603I (5 nm)/Cu2:LLP604 (20 nm)/PT74M 
               
               
                 (5 nm)/LET321:Liq (1:1, 25 nm)/Liq (1 nm)/Al (100 nm) 
               
            
           
           
               
               
               
               
               
               
            
               
                   
                 1 mA cm −2   
                 3 mA cm −2   
                 5 mA cm −2   
                   
                 LT@1000 cd m −2   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
            
               
                   
                 L 0   
                 LT50 
                 L 0   
                 LT50 
                 L 0   
                 LT50 
                   
                 LT90 
                 LT50 
               
               
                 Conc. 
                 [cd m −2 ] 
                 [h] 
                 [cd m −2 ] 
                 [h] 
                 [cd m −2 ] 
                 [h] 
                 n 
                 [h] 
                 [h] 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
            
               
                 2 wt/wt % 
                 3600 
                 132 
                 11000 
                 31.13 
                 19500 
                 14.14 
                 1.32 
                 52.97 
                 713.4 
               
               
                 4 wt/wt % 
                 4500 
                 112 
                 12300 
                 26.4 
                 21000 
                 12.2 
                 1.44 
                 64.94 
                 978.0 
               
               
                   
               
               
                 n denotes for acceleration factor in LT(L 1 ) = LT(L 0 ) × (L 0 /L 1 ) n   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 5b 
               
             
            
               
                   
               
               
                 Device data for Cu2 (same device structure as Table 5a) 
               
            
           
           
               
               
               
               
               
            
               
                   
                 CE [cd A −1 ] 
                 PE [lm W −1 ] 
                 EQE [%] 
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
            
               
                   
                 L 
                   
                 at 1000 
                   
                 at 1000 
                   
                 at 1000 
                 CIE 
                 λ max   
               
               
                 Cu2 
                 [cd m −2 ] 
                 Max 
                 cd m −2   
                 Max 
                 cd m −2   
                 Max 
                 cd m −2   
                 (x, y) 
                 [nm] 
               
               
                   
               
               
                 2 wt/wt % 
                 210000 
                 51.54 
                 49.69 
                 63.89 
                 44.98 
                 16.15 
                 15.60 
                 (0.30, 0.57) 
                 512 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 6 
               
             
            
               
                   
               
               
                 Device data for Cu3 
               
            
           
           
               
               
               
               
               
            
               
                   
                 CE [cd A −1 ] 
                 PE [lm W −1 ] 
                 EQE [%] 
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
            
               
                   
                 L 
                   
                 at 1000 
                   
                 at 1000 
                   
                 at 1000 
                 CIE 
                 λ max   
               
               
                 Cu3 
                 [cd m −2 ] 
                 Max 
                 cd m −2   
                 Max 
                 cd m −2   
                 Max 
                 cd m −2   
                 (x, y) 
                 [nm] 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
            
               
                 2 wt/wt % 
                 72500 
                 30.63 
                 24.94 
                 32.08 
                 11.73 
                 16.51 
                 13.44 
                 (0.54, 0.45) 
                 601 
               
               
                 4 wt/wt % 
                 46400 
                 19.49 
                 14.83 
                 17.87 
                 5.82 
                 14.48 
                 11.02 
                 (0.59, 0.41) 
                 622 
               
               
                 6 wt/wt % 
                 35000 
                 15.92 
                 11.37 
                 14.47 
                 4.17 
                 13.81 
                 9.87 
                 (0.60, 0.40) 
                 624 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 7 
               
             
            
               
                   
               
               
                 Device lifetime measurement for Cu3. Device structure: ITO/HAT-CN 
               
               
                 (5 nm)/PT-301 (160 nm)/PT-603I (5 nm)/Cu3: LLP604 (20 nm)/PT74M 
               
               
                 (5 nm)/LET321: Liq (1:1, 25 nm)/Liq (1 nm)/Al (100 nm). 
               
            
           
           
               
               
               
               
               
            
               
                   
                 1 mA cm −2   
                   
                 LT@1000 cd m −2   
                   
               
            
           
           
               
               
               
               
               
               
            
               
                   
                 L 0   
                 LT90 
                   
                 LT95 
                 LT90 
               
               
                 Conc. 
                 [cd m −2 ] 
                 [h] 
                 n 
                 [h] 
                 [h] 
               
               
                   
               
            
           
           
               
               
               
               
               
               
            
               
                 1 wt/wt % 
                 2600 
                 75.2 
                 1.78 
                 161 
                 412 
               
               
                 2 wt/wt % 
                 2600 
                 101 
                 1.78 
                 236 
                 553 
               
               
                 4 wt/wt % 
                 1880 
                 146 
                 1.78 
                 157 
                 450 
               
               
                   
               
               
                 n denotes for acceleration factor in LT(L 1 ) = LT(L 0 ) × (L 0 /L 1 ) n   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 8 
               
             
            
               
                   
               
               
                 Device data for Au1 
               
            
           
           
               
               
               
               
               
            
               
                   
                 CE [cd A −1 ] 
                 PE [lm W −1 ] 
                 EQE [%] 
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
            
               
                   
                 L 
                   
                 at 1000 
                   
                 at 1000 
                   
                 at 1000 
                 CIE 
                 λ max   
               
               
                 Au1 
                 [cd m −2 ] 
                 Max 
                 cd m −2   
                 Max 
                 cd m −2   
                 Max 
                 cd m −2   
                 (x, y) 
                 [nm] 
               
               
                   
               
               
                 2 wt/wt % 
                 176000 
                 61.63 
                 61.05 
                 72.83 
                 45.19 
                 19.66 
                 19.47 
                 (0.42, 0.55) 
                 554 
               
               
                 4 wt/wt % 
                 198000 
                 60.29 
                 57.26 
                 72.07 
                 39.98 
                 21.28 
                 20.21 
                 (0.47, 0.52) 
                 566 
               
               
                 6 wt/wt % 
                 202200 
                 52.37 
                 51.93 
                 56.29 
                 35.53 
                 16.70 
                 16.26 
                 (0.49, 0.50) 
                 572 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 9 
               
             
            
               
                   
               
               
                 Device lifetime measurement for Au1. Device structure: ITO/HAT-CN 
               
               
                 (5 nm)/PT-301 (160 nm)/PT-603I (5 nm)/Au1:LLP604 (30 nm)/PT74M 
               
               
                 (5 nm)/LET321:Liq (1:1, 25 nm)/Liq (1 nm)/Al (100 nm) 
               
            
           
           
               
               
               
               
               
               
            
               
                   
                 1 mA cm −2   
                 3 mA cm −2   
                 5 mA cm −2   
                   
                 LT@1000 cd m −2   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
            
               
                   
                 L 0   
                 LT50 
                 L 0   
                 LT50 
                 L 0   
                 LT50 
                   
                 LT90 
                 LT50 
               
               
                 Conc. 
                 [cd m −2 ] 
                 [h] 
                 [cd m −2 ] 
                 [h] 
                 [cd m −2 ] 
                 [h] 
                 n 
                 [h] 
                 [h] 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
            
               
                 2 wt/wt % 
                 3600 
                 135 
                 11000 
                 19.7 
                 17000 
                 8.96 
                 1.74 
                 1278 
                 15763 
               
               
                 4 wt/wt % 
                 3200 
                 76.1 
                 8900 
                 19.4 
                 15000 
                 9.68 
                 1.33 
                 355 
                 3763 
               
               
                 6 wt/wt % 
                 3400 
                 80.7 
                 11000 
                 17.9 
                 17000 
                 10.2 
                 1.29 
                 395 
                 4972 
               
               
                 8 wt/wt % 
                 3300 
                 69.3 
                 11200 
                 14.2 
                 17000 
                 8.76 
                 1.27 
                 305 
                 3913 
               
               
                   
               
               
                 n denotes for acceleration factor in LT(L 1 ) = LT(L 0 ) × (L 0 /L 1 ) n   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 9a 
               
             
            
               
                   
               
               
                 Device lifetime measurement for Au1. Device structure: 
               
               
                 ITO/HAT-CN (10 nm)/FSFA (60 nm)/NPB-BC (5 nm)/Au1:NPB- 
               
               
                 BC:Al (30 nm)/ANT-Biz (5 nm)/ANT-Biz:Liq (1:1, 
               
               
                 25 nm)/Liq (2 nm)/Al (100 nm). 
               
            
           
           
               
               
               
               
            
               
                   
                 LT@L 0   
                   
                 LT@1000 cd m −2   
               
            
           
           
               
               
               
               
               
               
               
            
               
                   
                 L 0   
                 LT97 
                 LT90 
                   
                 LT97 
                 LT90 
               
               
                 Conc. 
                 [cd m −2 ] 
                 [h] 
                 [h] 
                 n 
                 [h] 
                 [h] 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
            
               
                 6 
                 wt/wt % 
                 26000 
                 4.63 
                 18.3 
                 1.7 
                 1176 
                 4648 
               
               
                 10 
                 wt/wt % 
                 26000 
                 3.87 
                 20.0 
                 1.7 
                 984 
                 5080 
               
               
                   
               
               
                 n denotes for acceleration factor in LT(L 1 ) = LT(L 0 ) × (L 0 /L 1 ) n   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 10 
               
             
            
               
                   
               
               
                 Device data for Au2 in Device structure (I) 
               
            
           
           
               
               
               
               
               
            
               
                   
                 CE [cd A −1 ] 
                 PE [lm W −1 ] 
                 EQE [%] 
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
            
               
                   
                 L 
                   
                 at 1000 
                   
                 at 1000 
                   
                 at 1000 
                 CIE 
                 λ max   
               
               
                 Au2 
                 [cd m −2 ] 
                 Max 
                 cd m −2   
                 Max 
                 cd m −2   
                 Max 
                 cd m −2   
                 (x, y) 
                 [nm] 
               
               
                   
               
               
                 2 wt/wt % 
                 32600 
                 52.47 
                 41.36 
                 58.87 
                 29.53 
                 18.05 
                 14.22 
                 (0.26, 0.57) 
                 518 
               
               
                 4 wt/wt % 
                 50100 
                 61.54 
                 53.15 
                 66.17 
                 39.08 
                 20.49 
                 17.73 
                 (0.28, 0.58) 
                 519 
               
               
                 6 wt/wt % 
                 59100 
                 59.82 
                 53.87 
                 66.95 
                 39.34 
                 18.55 
                 16.76 
                 (0.29, 0.59) 
                 521 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 11 
               
             
            
               
                   
               
               
                 Device data for Au2 in Device structure (II) 
               
            
           
           
               
               
               
               
               
            
               
                   
                 CE [cd A −1 ] 
                 PE [lm W −1 ] 
                 EQE [%] 
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
            
               
                   
                 L 
                   
                 at 1000 
                   
                 at 1000 
                   
                 at 1000 
                 CIE 
                 λ max   
               
               
                 Au2 
                 [cd m −2 ] 
                 Max 
                 cd m −2   
                 Max 
                 cd m −2   
                 Max 
                 cd m −2   
                 (x, y) 
                 [nm] 
               
               
                   
               
               
                 2 wt/wt % 
                 10300 
                 38.00 
                 30.85 
                 35.11 
                 23.44 
                 16.15 
                 13.18 
                 (0.18, 0.35) 
                 488 
               
               
                 4 wt/wt % 
                 13400 
                 38.00 
                 35.36 
                 35.02 
                 27.78 
                 13.56 
                 12.63 
                 (0.23, 0.45) 
                 496 
               
               
                 8 wt/wt % 
                 22700 
                 44.82 
                 38.76 
                 41.74 
                 28.96 
                 16.27 
                 14.05 
                 (0.22, 0.45) 
                 494 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 12 
               
             
            
               
                   
               
               
                 Comparison with other Au(I) emitters 
               
            
           
           
               
               
               
               
               
               
            
               
                   
                   
                   
                 Current 
                 Current 
                 Current 
               
               
                   
                 Reported 
                 Reported 
                 data 
                 data 
                 data for 
               
               
                   
                 Gold(I) 
                 Gold(I) 
                 for Gold(I), 
                 for Gold(I), 
                 for Gold(I), 
               
               
                   
                 emitter 
                 emitter 
                 Au1 
                 Au2 
                 Au2 
               
               
                   
                   
               
            
           
           
               
               
               
               
               
               
            
               
                 CIE (x, y) 
                 EL λ max   
                 EL λ max   
                 yellow 
                 blue green 
                 green 
               
               
                   
                 ~510 nm 
                 ~530 nm 
                 (0.47, 0.52) 
                 (0.22, 0.45) 
                 (0.34, 0.55) 
               
               
                 Maximum 
                 44700 
                 73100 
                 198000 
                 22700 
                 230000 
               
               
                 Brightness 
               
               
                 (cd/m 2 ) 
               
               
                 Current 
                 73.0 
                 77.9 
                 57.3 
                 38.8 
                 51.7 
               
               
                 efficiency 
               
               
                 @1000 
               
               
                 cd/m 2   
               
               
                 (cd/A) 
               
               
                 Power 
                 37.0 
                 35.5 
                 40.0 
                 29.0 
                 54.1 
               
               
                 efficiency 
               
               
                 @1000 
               
               
                 cd/m 2   
               
               
                 (lm/W) 
               
               
                 External 
                 25.2 
                 24.5 
                 20.2 
                 14.1 
                 15.9 
               
               
                 quantum 
               
               
                 efficiency 
               
               
                 @1000 
               
               
                 cd/m 2   
               
               
                 (%) 
               
               
                 LT 
                 @100 cd 
                 NA 
                 @1000 cd 
                 NA 
                 @1000 cd 
               
               
                   
                 m −2   
                   
                 m −2   
                   
                 m −2   
               
               
                   
                 LT95 ~2 h 
                   
                 LT90 ~5080 h 
                   
                 LT90 ~117 h 
               
               
                   
                   
                   
                   
                   
                 LT50 ~1446 h 
               
               
                 Reference 
                 
                   Science 
                 
                 
                   Science 
                 
               
               
                   
                 2017, 356, 159-163; 
                 2017, 356, 159-163 
               
               
                   
                 
                   Nat 
                 
               
               
                   
                 
                   commun 
                 
               
               
                   
                 2020, 11, 1758 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 13 
               
             
            
               
                   
               
               
                 Comparison with other Cu(I) emitters 
               
            
           
           
               
               
               
               
               
               
            
               
                   
                 Reported 
                 Reported 
                 Current 
                 Current 
                 Current 
               
               
                   
                 Copper(I) 
                 Copper(I) 
                 data 
                 data 
                 data 
               
               
                   
                 emitter 
                 emitter 
                 for Cu1 
                 for Cu2 
                 for Cu3 
               
               
                   
                   
               
            
           
           
               
               
               
               
               
               
            
               
                 CIE (x, y) 
                 EL λ max   
                 EL λ max   
                 yellow 
                 green 
                 orange 
               
               
                   
                 ~543 nm 
                 ~505 nm 
                 (0.43, 0.55) 
                 (0.30, 0.57) 
                 (0.58, 0.42) 
               
               
                 Maximum 
                 54000  
                 7790 
                 153400; 
                 210000 
                 155000 
               
               
                 Brightness 
                   
                   
                 222200 
               
               
                 (cd/m 2 ) 
               
               
                 Current 
                 NA 
                 29.0 
                 55.8; 
                 49.69 
                 21.3 
               
               
                 efficiency 
                   
                   
                 43.7 
               
               
                 @1000 
               
               
                 cd/m 2   
               
               
                 (cd/A) 
               
               
                 Power 
                 NA 
                 9.3 
                 42.5; 
                 44.98 
                 12.4 
               
               
                 efficiency 
                   
                   
                 29.1 
               
               
                 @1000 
               
               
                 cd/m 2   
               
               
                 (lm/W) 
               
               
                 External 
                 −19 
                 9.2 
                 18.7; 
                 15.60 
                 13.8 
               
               
                 quantum 
                   
                   
                 18.3 
               
               
                 efficiency 
               
               
                 @1000 
               
               
                 cd/m 2   
               
               
                 (%) 
               
               
                 LT 
                 NA 
                 NA 
                 @1000 cd 
                 @1000 cd 
                 @1000 cd 
               
               
                   
                   
                   
                 m −2   
                 m −2   
                 m −2   
               
               
                   
                   
                   
                 LT90 ~362 h 
                 LT90 ~65 h 
                 LT90 ~1160 h 
               
               
                   
                   
                   
                 LT50 ~9230 h 
                 LT50 ~978h 
               
               
                 Reference 
                 
                   J. Am. 
                 
                 
                   Science 
                 
               
               
                   
                 
                   Chem. Soc. 
                 
                 2017, 356, 
               
               
                   
                 2019, 141, 
                 159-163 
               
               
                   
                 3576-3588 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 14 
               
             
            
               
                   
               
               
                 Device data for Cu3 in Device structure (II): ITO/HAT-CN (5 nm)/PT- 
               
               
                 301 (160 nm)/EB (5 nm)/Cu3:RH (40 nm)/HB (5 nm)/ZADN:Liq (35:65, 
               
               
                 35 nm)/Liq (1 nm)/Al (100 nm). (cf. FIGS. 14A-14D) 
               
            
           
           
               
               
               
               
               
            
               
                   
                 CE [cd A −1 ] 
                 PE [lm W −1 ] 
                 EQE [%] 
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
            
               
                   
                 L 
                   
                 at 1000 
                   
                 at 1000 
                   
                 at 1000 
                 CIE 
                 λ max   
               
               
                 Cu3 
                 [cd m −2 ] 
                 Max 
                 cd m −2   
                 Max 
                 cd m −2   
                 Max 
                 cd m −2   
                 (x, y) 
                 [nm] 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
            
               
                 2 wt/wt % 
                 155000 
                 22.11 
                 21.29 
                 21.98 
                 12.39 
                 14.35 
                 13.82 
                 (0.58, 0.42) 
                 619 
               
               
                 4 wt/wt % 
                 117000 
                 17.28 
                 16.28 
                 14.45 
                 8.12 
                 13.72 
                 12.93 
                 (0.61, 0.39) 
                 627 
               
               
                 6 wt/wt % 
                 40000 
                 14.16 
                 13.46 
                 11.90 
                 6.13 
                 11.85 
                 11.26 
                 (0.61, 0.39) 
                 628 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 15 
               
             
            
               
                   
               
               
                 Device lifetime measurement for Cu3. Device structure (II): 
               
               
                 ITO/HAT-CN (5 nm)/PT-301 (160 nm)/EB (5 nm)/Cu3:RH (40 nm)/HB 
               
               
                 (5 nm)/ZADN:Liq (35:65, 35 nm)/Liq (1 nm)/Al (100 nm) 
               
            
           
           
               
               
               
               
            
               
                   
                 5 mA cm −2   
                   
                 LT@1000 cd m −2   
               
            
           
           
               
               
               
               
               
               
               
            
               
                   
                 L 0   
                 LT95 
                 LT90 
                   
                 LT95 
                 LT90 
               
               
                 Conc. 
                 [cd m −2 ] 
                 [h] 
                 [h] 
                 n 
                 [h] 
                 [h] 
               
               
                   
               
               
                 2 wt/wt % 
                 9800 
                 13.3 
                 32.3 
                 1.57 
                 478 
                 1160 
               
               
                   
               
               
                 n denotes for acceleration factor in LT(L 1 ) = LT(L 0 ) × (L 0 /L 1 ) n   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 16 
               
             
            
               
                   
               
               
                 Device data for Cu4 in Device structure (I): ITO/HAT-CN 
               
               
                 (5 nm)/TAPC (40 nm)/TCTA (10 nm)/TCTA:TPBi:Cu4 (20 nm)/TPBi 
               
               
                 (50 nm)/LiF (1 nm)/Al (100 nm). (cf FIGS. 15A-15D) 
               
            
           
           
               
               
               
               
               
            
               
                   
                 CE [cd A −1 ] 
                 PE [lm W −1 ] 
                 EQE [%] 
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
            
               
                   
                 L 
                   
                 at 1000 
                   
                 at 1000 
                   
                 at 1000 
                 CIE 
                 λ max   
               
               
                 Cu4 
                 [cd m −2 ] 
                 Max 
                 cd m −2   
                 Max 
                 cd m −2   
                 Max 
                 cd m −2   
                 (x, y) 
                 [nm] 
               
               
                   
               
               
                 2 wt/wt % 
                 26300 
                 40.99 
                 35.74 
                 46.00 
                 18.71 
                 17.95 
                 15.65 
                 (0.50, 0.49) 
                 580 
               
               
                 4 wt/wt % 
                 21000 
                 32.51 
                 28.59 
                 39.37 
                 13.82 
                 17.23 
                 15.15 
                 (0.54, 0.46) 
                 595 
               
               
                 6 wt/wt % 
                 16800 
                 32.67 
                 26.30 
                 33.11 
                 12.27 
                 17.15 
                 13.88 
                 (0.54, 0.46) 
                 593 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 17 
               
             
            
               
                   
               
               
                 Device data for Cu4 in Device structure (II): ITO/HAT-CN (5 nm)/PT- 
               
               
                 301 (160 nm)/PT-603I (5 nm)/Cu4:LLP604 (20 nm)/PT74M (5 nm)/LET321:Liq 
               
               
                 (1:1, 25 nm)/Liq (1 nm)/Al (100 nm). (cf. FIGS. 16A-16D) 
               
            
           
           
               
               
               
               
               
            
               
                   
                 CE [cd A −1 ] 
                 PE [lm W −1 ] 
                 EQE [%] 
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
            
               
                   
                 L 
                   
                 at 1000 
                   
                 at 1000 
                   
                 at 1000 
                 CIE 
                 λ max   
               
               
                 Cu4 
                 [cd m −2 ] 
                 Max 
                 cd m −2   
                 Max 
                 cd m −2   
                 Max 
                 cd m −2   
                 (x, y) 
                 [nm] 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
            
               
                 2 wt/wt % 
                 118000 
                 24.46 
                 21.20 
                 31.71 
                 18.47 
                 10.57 
                 9.15 
                 (0.53, 0.46) 
                 593 
               
               
                 4 wt/wt % 
                 97000 
                 18.82 
                 17.51 
                 24.70 
                 14.45 
                 9.98 
                 9.33 
                 (0.57, 0.43) 
                 603 
               
               
                 6 wt/wt % 
                 91000 
                 17.43 
                 16.25 
                 22.43 
                 12.92 
                 9.69 
                 9.05 
                 (0.58, 0.42) 
                 604 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 18 
               
             
            
               
                   
               
               
                 Device lifetime measurement for Cu4. Device structure 
               
               
                 (II): ITO/HAT-CN (5 nm)/PT-301 (160 nm)/PT-603I 
               
               
                 (5 nm)/Cu4:LLP604 (20 nm)/PT74M (5 nm)/LET321:Liq 
               
               
                 (1:1, 25 nm)/Liq (1 nm)/Al (100 nm). 
               
            
           
           
               
               
               
               
            
               
                   
                 1 mA cm −2   
                   
                 LT@1000 cd m −2   
               
            
           
           
               
               
               
               
               
               
               
            
               
                   
                 L 0   
                 LT95 
                 LT90 
                   
                 LT95 
                 LT90 
               
               
                 Conc. 
                 [cd m −2 ] 
                 [h] 
                 [h] 
                 n 
                 [h] 
                 [h] 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
            
               
                 2 wt/wt % 
                 1400 
                 15.2 
                 53.3 
                 1.80 
                 27.9 
                 79.5 
               
               
                 4 wt/wt % 
                 1100 
                 6.69 
                 41.4 
                 1.48 
                 7.71 
                 47.6 
               
               
                 6 wt/wt % 
                 1000 
                 4.01 
                 27.8 
                 1.22 
                 4.01 
                 27.8 
               
               
                   
               
               
                 n denotes for acceleration factor in LT(L 1 ) = LT(L 0 ) × (L 0 /L 1 ) n   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 19 
               
             
            
               
                   
               
               
                 Device data for Au2 in Device structure (III): ITO/HAT-CN (5 nm)/PT- 
               
               
                 301 (160 nm)/PT-603I (5 nm)/Au2:LLP604 (20 nm)/PT74M (5 nm)/LET321:Liq 
               
               
                 (1:1, 25 nm)/Liq (1 nm)/Al (100 nm). (cf. FIGS. 17A-17D) 
               
            
           
           
               
               
               
               
               
            
               
                   
                 CE [cd A −1 ] 
                 PE [lm W −1 ] 
                 EQE [%] 
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
            
               
                   
                 L 
                   
                 at 1000 
                   
                 at 1000 
                   
                 at 1000 
                 CIE 
                 λ max   
               
               
                 Au2 
                 [cd m −2 ] 
                 Max 
                 cd m −2   
                 Max 
                 cd m −2   
                 Max 
                 cd m −2   
                 (x, y) 
                 [nm] 
               
               
                   
               
               
                 2 wt/wt % 
                 212000 
                 49.34 
                 44.40 
                 62.02 
                 49.45 
                 15.15 
                 13.92 
                 (0.32, 0.55) 
                 532 
               
               
                 4 wt/wt % 
                 250000 
                 53.77 
                 49.95 
                 67.58 
                 52.95 
                 16.51 
                 15.57 
                 (0.33, 0.55) 
                 534 
               
               
                 8 wt/wt % 
                 230000 
                 55.23 
                 51.68 
                 69.41 
                 54.13 
                 16.96 
                 15.86 
                 (0.34, 0.55) 
                 538 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 20 
               
             
            
               
                   
               
               
                 Device lifetime measurement for Au2. Device structure (III): ITO/HAT-CN 
               
               
                 (5 nm)/PT-301 (160 nm)/PT-603I (5 nm)/Au2:LLP604 (20 nm)/PT74M 
               
               
                 (5 nm)/LET321:Liq (1:1, 25 nm)/Liq (1 nm)/Al (100 nm). 
               
            
           
           
               
               
            
               
                   
                 LT@1000 cd m −2   
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                   
                 L 0   
                 LT95 
                 LT90 
                 LT50 
                   
                 LT95 
                 LT90 
                 LT50 
               
               
                 Conc. 
                 [cd m −2 ] 
                 [h] 
                 [h] 
                 [h] 
                 n 
                 [h] 
                 [h] 
                 [h] 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                 2 wt/wt % 
                 17500 
                 0.67 
                 1.56 
                 19.2 
                 1.51 
                 50.47 
                 117.5 
                 1446 
               
               
                 4 wt/wt % 
                 21000 
                 0.86 
                 1.96 
                 22.8 
                 1.31 
                 46.41 
                 105.7 
                 1230 
               
               
                 8 wt/wt % 
                 21200 
                 0.66 
                 1.55 
                 18.9 
                 1.28 
                 32.90 
                 77.28 
                 940 
               
               
                   
               
               
                 n denotes for acceleration factor in LT(L 1 ) = LT(L 0 ) × (L 0 /L 1 ) n   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 21 
               
             
            
               
                   
               
               
                 Device lifetime measurement for Au complex with 3,5- 
               
               
                 dimethylphenyl group. a  Device structure: ITO/HAT-CN (5 nm)/ 
               
               
                 PT-301 (160 nm)/Spiro-3-BFP (15 nm)/ 
               
               
                 Au complex: DMIC-TRz:DMIC-Cz (15 nm)/LET003 
               
               
                 (20 nm)/Liq (1 nm)/Al (100 nm) 
               
            
           
           
               
               
               
               
               
               
            
               
                   
                 L 0    
                 LT95  
                 LT50 
                   
                 LT@1000 cd m -2   
               
            
           
           
               
               
               
               
               
               
               
            
               
                   
                 [cd m -2 ]  
                 [h]  
                 [h]  
                 n  
                 LT95 [h]  
                 LT50 [h] 
               
               
                   
               
               
                 2wt/wt % 
                 5400 
                 2.43 
                 97 
                 1.7 
                 42.7  
                 1705 
               
               
                   
               
               
                 n denotes for acceleration factor in LT(L 1 ) = LT(L 0 ) × (L 0 /L 1 ) n   
               
               
                 
                   a 
                 
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 22 
               
             
            
               
                   
               
               
                 Device data for Cu6 in TCTA:DPEPO co-host. Device structure: 
               
               
                 ITO/HAT-CN (5 nm)/TAPC (40 nm)/TCTA (10 nm)/TCTA:DPEPO:Cu6 
               
               
                 (20 nm)/DPEPO(10 nm)/TPBi (40 nm)/LiF (1.2 nm)/Al (100 nm). 
               
            
           
           
               
               
               
               
               
            
               
                   
                 CE [cd A −1 ] 
                 PE [lm W −1 ] 
                 EQE [%] 
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
            
               
                   
                 L max   
                   
                 at 1000 
                   
                 at 1000 
                   
                 at 1000 
                 CIE 
                 λ max   
               
               
                 Cu6 
                 [cd m −2 ] 
                 Max 
                 cd m −2   
                 Max 
                 cd m −2   
                 Max 
                 cd m −2   
                 (x, y) 
                 [nm] 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
            
               
                 2 wt/wt % 
                 9110 
                 30.3 
                 22.8 
                 24.7 
                 11.1 
                 21.2 
                 15.9 
                 (0.14, 0.19) 
                 472 
               
               
                 4 wt/wt % 
                 15600 
                 36.4 
                 28.8 
                 32.6 
                 13.9 
                 23.6 
                 18.7 
                 (0.14, 0.22) 
                 474 
               
               
                 6 wt/wt % 
                 22700 
                 33.9 
                 32.1 
                 29.1 
                 15.5 
                 20.0 
                 18.9 
                 (0.14, 0.25) 
                 478 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 23 
               
             
            
               
                   
               
               
                 Device lifetime measurement for Cu6. Device 
               
               
                 structure: ITO/HAT-CN (10 nm)/BPBPA (120 
               
               
                 nm)/mCBP (10 nm)/mCBP:SiCzTrz:Cu6 (30 
               
               
                 nm)/SF3-TRz (5 nm)/SF3-TRz:Liq (1:1, 
               
               
                 25 nm)/Liq (2 nm)/Al (100 nm). 
               
            
           
           
               
               
               
               
            
               
                   
                 LT@L 0   
                   
                 LT@1000 cd m −2   
               
            
           
           
               
               
               
               
               
               
               
            
               
                   
                 L 0   
                 LT90 
                 LT50 
                   
                 LT90 
                 LT50 
               
               
                 Conc. 
                 [cd m −2 ] 
                 [h] 
                 [h] 
                 n 
                 [h] 
                 [h] 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
            
               
                 2 wt/wt % 
                 6100 
                 0.36 
                 5.31 
                 1.51 
                 5.52 
                 81.5 
               
               
                 4 wt/wt % 
                 6600 
                 0.36 
                 5.86 
                 1.56 
                 6.84 
                 111 
               
               
                 8 wt/wt % 
                 7600 
                 0.4 
                 7.46 
                 1.66 
                 11.6 
                 216 
               
               
                   
               
               
                 n denotes for acceleration factor in LT(L 1 ) = LT(L 0 ) × (L 0 /L 1 ) n   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 24 
               
             
            
               
                   
               
               
                 Device data for hyper-fluorescence OLED based on Cu6 and ν-DABNA in mCBP. 
               
               
                 Device structure: ITO/HAT-CN (10 nm)/BPBPA (120 nm)/mCBP (10 nm)/mCBP:Cu6:ν-DABNA 
               
               
                 (20 nm)/SF3-TRz (5 nm)/SF3-TRz:Liq (1:1, 25 nm)/Liq (2 nm)/Al (100 nm). 
               
            
           
           
               
               
               
            
               
                   
                 EQE [%] 
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
            
               
                   
                 L max   
                 CE max   
                 PE max   
                   
                 at 1000 
                 at 10000 
                 CIE 
                 λ max   
                 FWHM 
               
               
                 Cu6:ν-DABNA 
                 [cd m −2 ] 
                 [cd A − 1] 
                 [lm W −1 ] 
                 Max 
                 cd m −2   
                 cd m −2   
                 (x, y) 
                 [nm] 
                 [nm] 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
            
               
                 8:0 wt/wt % 
                 17000 
                 16.8 
                 16.3 
                 8.63 
                 7.66 
                 6.63 
                 (0.18, 0.29) 
                 477 
                 92 
               
               
                 8:1 wt/wt % 
                 16500 
                 15.6 
                 16.1 
                 9.70 
                 8.51 
                 6.82 
                 (0.16, 0.24) 
                 470 
                 23 
               
               
                 8:2 wt/wt % 
                 15200 
                 14.3 
                 12.8 
                 10.2 
                 8.42 
                 6.13 
                 (0.15, 0.20) 
                 470 
                 19 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 25 
               
             
            
               
                   
               
               
                 Device lifetime measurement for hyper-fluorescence 
               
               
                 OLED based on Cu6 and ν-DABNA in mCBP. Device 
               
               
                 structure: ITO/HAT-CN (10 nm)/BPBPA (120 nm)/mCBP 
               
               
                 (10 nm)/mCBP: Cu6: ν-DABNA (20 nm)/SF3-TRz (5 
               
               
                 nm)/SF3-TRz: Liq (1:1, 25 nm)/Liq (2 nm)/Al (100 nm). 
               
            
           
           
               
               
               
               
               
            
               
                 Cu6: 
                 L 0   
                 LT90@L 0   
                   
                 LT90@1000 cd 
               
               
                 ν-DABNA 
                 [cd m −2 ] 
                 [h] 
                 n 
                 m −2  [h] 
               
               
                   
               
            
           
           
               
               
               
               
               
            
               
                 8:0 wt/wt % 
                 4000 
                 0.48 
                 1.64 
                 4.7 
               
               
                 8:1 wt/wt % 
                 6100 
                 0.33 
                 1.66 
                 6.6 
               
               
                 8:2 wt/wt % 
                 5000 
                 0.76 
                 1.72 
                 12.2 
               
               
                   
               
               
                 n denotes for acceleration factor in LT(L 1 ) = LT(L 0 ) × (L 0 /L 1 ) n   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 26 
               
             
            
               
                   
               
               
                 Device data for Cu7 in DMIC-Cz:DMIC-Trz co-host. Device structure: 
               
               
                 ITO/HAT-CN (10 nm)/BPBOA (80 nm)/FSF4A (5 nm)/DMIC-Cz:DMIC-Trz:Cu7 
               
               
                 (30 nm)/ANT-Biz (5 nm)/ANT-Biz:Liq (25 nm)/Liq (2 nm)/Al (100 nm). 
               
            
           
           
               
               
               
               
            
               
                   
                 CE [cd A −1 ] 
                 EQE [%] 
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
            
               
                   
                 L max   
                   
                 at 1000 
                 at 10000 
                   
                 at 1000 
                 at 10000 
                 CIE 
                   
               
               
                 Cu7 
                 [cd m −2 ] 
                 Max 
                 cd m −2   
                 cd m −2   
                 Max 
                 cd m −2   
                 cd m −2   
                 (x, y) 
                 λ max   
               
               
                   
               
               
                 2 wt/wt % 
                 190000 
                 27.3 
                 27.2 
                 26.3 
                 14.7 
                 14.7 
                 14.2 
                 (0.56, 0.44) 
                 600 
               
               
                 4 wt/wt % 
                 160000 
                 25.6 
                 25.4 
                 24.1 
                 14.4 
                 14.2 
                 13.5 
                 (0.57, 0.43) 
                 601 
               
               
                 6 wt/wt % 
                 113000 
                 18.9 
                 18.4 
                 16.8 
                 11.9 
                 11.6 
                 10.6 
                 (0.58, 0.42) 
                 604 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 27 
               
             
            
               
                   
               
               
                 Device data for hyper-fluorescence OLED based on Cu7 and MR-R in RH. Device structure: ITO/HAT-CN (10 
               
               
                 nm)/HT (40 nm)/EB (5 nm)/Cu7:MR-R:RH (40 nm)/HB (5 nm)/ZADN:Liq (35:65) (35 nm)/Liq (2 nm)/Al (100 nm) 
               
            
           
           
               
               
               
               
            
               
                   
                 CE [cd A −1 ] 
                 EQE [%] 
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
            
               
                   
                 L max   
                   
                 at 1000 
                 at 10000 
                   
                 at 1000 
                 at 10000 
                 CIE 
                 λ max   
                 FWHM 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
            
               
                 Cu7:MR-R 
                 [cd m −2 ] 
                 Max 
                 cd m −2   
                 cd m −2   
                 Max 
                 cd m −2   
                 cd m −2   
                 (x, y) 
                 [nm] 
                 [nm] 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
               
            
               
                 10:0 
                 wt/wt % 
                 109000 
                 18.7 
                 18.5 
                 17.6 
                 15.5 
                 15.4 
                 14.6 
                 (0.59, 0.41) 
                 612 
                 125 
               
               
                 10:0.3 
                 wt/wt % 
                 124000 
                 22.7 
                 22.6 
                 21.7 
                 14.5 
                 14.4 
                 13.8 
                 (0.61, 0.39) 
                 613 
                 36 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 28 
               
             
            
               
                   
               
               
                 Device lifetime measurement for OLEDs based on Cu7 
               
               
                 and MR-R in RH. Device structure: ITO/HAT-CN (10 nm)/HT 
               
               
                 (40 nm)/EB (5 nm)/Cu7:MR-R:RH (40 nm)/HB (5 nm)/ZADN:Liq 
               
               
                 (35:65) (35 nm)/Liq (2 nm)/Al (100 nm). 
               
            
           
           
               
               
               
               
            
               
                   
                 LT@L 0   
                   
                 LT@1000 cd m −2   
               
            
           
           
               
               
               
               
               
               
               
            
               
                   
                 L 0   
                 LT95 
                 LT90 
                   
                 LT95 
                 LT90 
               
            
           
           
               
               
               
               
               
               
               
            
               
                 Cu7:MR-R 
                 [cd m −2 ] 
                 [h] 
                 [h] 
                 n 
                 [h] 
                 [h] 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
            
               
                 10:0 
                 wt/wt % 
                 8000 
                 29.9 
                 72 
                 1.7 
                 1026 
                 2462 
               
               
                 10:0.3 
                 wt/wt % 
                 8000 
                 46.5 
                 109 
                 1.7 
                 1595 
                 3740 
               
               
                   
               
               
                 n denotes for acceleration factor in LT(L 1 ) = LT(L 0 ) × (L 0 /L 1 ) n   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 29 
               
             
            
               
                   
               
               
                 Device data for hyper-fluorescence OLEDs based on Au3 and BN-2 in mCBP. 
               
               
                 Device structure: ITO/HAT-CN (5 nm)/TAPC (40 nm)/mCBP (10 nm)/Au3:BN- 
               
               
                 2:mCBP (20 nm)/PPF (10 nm)/TmPyPb (40 nm)/LiF (1.2 nm)/Al (100 nm). 
               
            
           
           
               
               
               
            
               
                   
                 EQE [%] 
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
            
               
                   
                 L max   
                 CE max   
                 PE max   
                   
                 at 1000 
                 at 10000 
                 CIE 
                 λ max   
                 FWHM 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
            
               
                 Au3:BN-2 
                 [cd m −2]   
                 [cd A −1 ] 
                 [lm W −1 ] 
                 Max 
                 cd m −2   
                 cd m −2   
                 (x, y) 
                 [nm] 
                 [nm] 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
            
               
                 6:1 
                 wt/wt % 
                 256000 
                 92.2 
                 90.9 
                 25.3 
                 19.1 
                 16.2 
                 (0.29, 0.65) 
                 41 
                 535 
               
               
                 10:0.6 
                 wt/wt % 
                 247000 
                 86.4 
                 76.8 
                 21.7 
                 19.0 
                 15.7 
                 (0.29, 0.66) 
                 41 
                 536 
               
               
                 6:0 
                 wt/wt % 
                 187000 
                 71.2 
                 63.6 
                 23.0 
                 21.4 
                 19.6 
                 (0.25, 0.57) 
                 72 
                 514 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 30 
               
             
            
               
                   
               
               
                 Device data for OLEDs based on Au5 in mCBP:CzSiTrz co-host. 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). 
               
            
           
           
               
               
               
            
               
                   
                 EQE [%] 
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
            
               
                   
                 L max   
                 CE max   
                 PE max   
                   
                 at 1000 
                 at 10000 
                 CIE 
                 λ max   
                 FWHM 
               
               
                 Au5 
                 [cd m −2 ] 
                 [cd A −1 ] 
                 [lm W −1 ] 
                 Max 
                 cd m −2   
                 cd m −2   
                 (x, y) 
                 [nm] 
                 [nm] 
               
               
                   
               
               
                 2 wt/wt % 
                 183000 
                 69.3 
                 66.0 
                 20.8 
                 19.1 
                 17.5 
                 (0.32, 0.56) 
                 533 
                 94 
               
               
                 4 wt/wt % 
                 300000 
                 65.6 
                 58.9 
                 19.4 
                 18.6 
                 16.9 
                 (0.35, 0.57) 
                 543 
                 96 
               
               
                 8 wt/wt % 
                 195000 
                 70.8 
                 67.4 
                 20.7 
                 19.0 
                 17.4 
                 (0.37, 0.57) 
                 543 
                 94 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 31 
               
             
            
               
                   
               
               
                 Device lifetime measurement for Au5. 
               
               
                 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). 
               
            
           
           
               
               
               
               
            
               
                   
                 LT@L 0   
                   
                 LT@1000 cd m −2   
               
            
           
           
               
               
               
               
               
               
               
            
               
                   
                 L 0   
                 LT90 
                 LT70 
                   
                 LT90 
                 LT70 
               
               
                 Conc. 
                 [cd m −2 ] 
                 [h] 
                 [h] 
                 n 
                 [h] 
                 [h] 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
            
               
                 2 wt/wt % 
                 17500 
                 0.99 
                 5.87 
                 1.74 
                 144 
                 854 
               
               
                 4 wt/wt % 
                 6000 
                 2.36 
                 15.0 
                 1.69 
                 49 
                 310 
               
               
                 8 wt/wt % 
                 18000 
                 0.60 
                 3.13 
                 1.56 
                 54 
                 284 
               
               
                   
               
               
                 n denotes for acceleration factor in LT(L 1 ) = LT(L 0 ) × (L 0 /L 1 ) n   
               
            
           
         
       
     
     Unless defined otherwise, all technical and scientific terms used herein have the same meanings as commonly understood by one of skill in the art to which the disclosed invention belongs. Publications cited herein and the materials for which they are cited are specifically incorporated by reference. Further, unless otherwise indicated, use of the expression “wt %” refers to “wt/wt %.” 
     Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments of the invention described herein. Such equivalents are intended to be encompassed by the following claims.