Granted Patent B2

US 12,520,715 · App. 17/811,422 · Granted Jan 6, 2026

Inventors: Tian-Yi Li (Los Angeles, CA); Peter I. Djurovich (Long Beach, CA); Mark E. Thompson (Anaheim, CA)

H10K85/371C07F1/005C07F1/08C09K11/06C09K2211/188H10K50/11

Abstract

Claims (94)

1 . A compound represented by the following Formula I:

wherein M 1 is selected from the group consisting of Au(I), Ag(I), and Cu(I);

L is a carbene coordinated to the metal M 1 ;

Z is a monoanionic ligand;

E 1 is an electron accepting group;

n is an integer from 1 to the maximum allowable substitution on L, wherein when n is greater than 1, each E 1 may be the same or different;

E 1 , L, and Z may each be substituted with one or more substituents independently selected from the group consisting of hydrogen, deuterium, halogen, pseudohalogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, amide, hydroxyl, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, heteroalkynyl, aryl, heteroaryl, nitro, nitrile, isonitrile, sulfanyl, boryl, acyl, carboxylic acid, benzoyl, ether, ester, vinyl, ketone, sulfinyl, sulfonyl, cyano, phosphino, and combinations thereof; wherein any two adjacent substituents may together join to form a ring.

2 . The compound of claim 1 , wherein E 1 is selected from the group consisting of a nitrogen-containing heterocyclic ring and a carbocyclic aromatic ring optionally having at least one electron-withdrawing substituent.

3 . The compound of claim 1 , wherein E 1 is a nitrogen-containing heterocyclic ring selected from the group consisting of aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, aza-benzofuran, aza-benzothiophene, aza-benzoselenophene, aza-carbazole, aza-indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, aza-xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, selenophenodipyridine, 1,2-azaborine, 1,3-azaborine, 1,4-azaborine, borazine, and aza-analogs thereof; wherein E 1 is optionally further substituted.

4 . The compound of claim 1 , wherein E 1 is a nitrogen-containing heterocyclic ring fused to the carbene L.

5 . The compound of claim 1 , wherein E 1 is an aromatic ring having at least one electron-withdrawing substituent selected from the group consisting of halogen, pseudohalogen, haloalkyl, halocycloalkyl, heteroalkyl, amide, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, heteroalkynyl, aryl, heteroaryl, nitro, nitrile, isonitrile, sulfanyl, boryl, acyl, carboxylic acid, benzoyl, ester, vinyl, ketone, sulfinyl, sulfonyl, cyano, phosphino, and combinations thereof; wherein E 1 is optionally further substituted.

6 . The compound of claim 1 , wherein L is selected from the group consisting of Formula A, Formula B, Formula C, Formula D, Formula E, and Formula F;

wherein

each X 1 to X 4 independently represents NR 1 , CR 1 R 2 , C═O, C═S, O, or S; and

each occurrence of R 1 and R 2 is independently selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, boryl, acyl, carboxylic acid, ether, ester, sulfinyl, sulfonyl, cyano, phosphino, and combinations thereof;

wherein at least one substituent R 1 and R 2 comprises an electron accepting group;

wherein any two adjacent R 1 and R 2 are optionally joined or fused together to form a ring which is optionally substituted,

wherein each X 1 and X 4 independently represents N, CR 1 R 2 , SiR 1 , SiR 1 R 2 , B, BR 1 , BR 1 R 2 , O, or S; and

each X 2 and X 3 independently represents CR 1 , CR 1 R 2 , SiR 1 , N, P, B, O, or S;

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

wherein at least one substituent R 1 and R 2 comprises an electron accepting group;

wherein any two adjacent R 1 and R 2 are optionally joined or fused together to form a ring which is optionally substituted; and

the dashed line inside the five-member ring represents zero or one double-bond,

wherein each X 1 and X 2 independently represents NR 1 , CR 1 R 2 , O, or S;

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

wherein at least one substituent R 1 and R 2 comprises an electron accepting group;

wherein any two adjacent R 1 and R 2 are optionally joined or fused together to form a ring which is optionally substituted,

wherein

each X 1 to X 5 independently represents N, P, NR 1 , PR 1 , B, BR 1 , CR 1 , SiR 1 , CR 1 R 2 , SiR 1 R 2 , C═O, C═S, O, or S;

n is 0 or 1;

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

wherein at least one substituent R 1 and R 2 comprises an electron accepting group; and

wherein any two adjacent R 1 and R 2 are optionally joined or fused together to form a ring which is optionally substituted;

wherein

each X 1 and X 4 independently represents NR 1 , CR 1 , SiR 1 , CR 1 R 2 , SiR 1 R 2 , PR 1 , BR 1 , C═O, C═S, O, or S;

each X 2 and X 3 is independently present or absent, and if present, independently represents H, NR 1 R 2 , CR 1 R 2 , C═O, C═S, O, or S;

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

wherein at least one substituent R 1 and R 2 comprises an electron accepting group; and

wherein any two adjacent R 1 and R 2 are optionally joined or fused together to form a ring which is optionally substituted

wherein each occurrence of X 1 to X 8 independently represents N, P, NR 1 , PR 1 , B, BR 1 , CR 1 , SiR 1 , CR 1 R 2 , SiR 1 R 2 , C═O, C═S, O, or S;

n is 1 or 2;

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

wherein at least one substituent R 1 and R 2 comprises an electron accepting group; and

wherein any two adjacent R 1 and R 2 are optionally joined or fused together to form a ring which is optionally substituted.

7 . The compound of claim 1 , wherein L is represented by one of the following structures:

wherein each X 1 and X 2 independently represents NR 1 , CR 1 , SiR 1 , CR 1 R 2 , SiR 1 R 2 , C═O, C═S, O, or S;

each X 3 and X 4 independently represents N, P, NR 1 , PR 1 , B, BR 1 , CR 1 , SiR 1 , CR 1 R 2 , SiR 1 R 2 , C═O, C═S, O, or S;

Y represents N, P, CR 1 , or SiR 1 ;

each Y 1 and Y 2 independently represents O, S, NR 1 , or CR 1 R 2

W represents O, NR 1 , or S;

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

wherein at least one substituent R 1 and R 2 comprises an electron accepting group; and

wherein any two adjacent R 1 and R 2 are optionally joined or fused together to form a ring which is optionally substituted.

8 . The compound of claim 1 , wherein L is represented by one of the following structures:

wherein each R is independently selected from the group consisting of hydrogen, deuterium, halogen, pseudohalogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, amide, hydroxyl, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, heteroalkynyl, aryl, heteroaryl, nitro, nitrile, isonitrile, sulfanyl, boryl, acyl, carboxylic acid, benzoyl, ether, ester, vinyl, ketone, sulfinyl, sulfonyl, cyano, phosphino, and combinations thereof; wherein any two adjacent substituents may together join to form a ring.

9 . The compound of claim 1 , wherein L is represented by one of the following structures:

wherein each X represents S, O, C(R) 2 , NR, or PR;

wherein each W represents an electron withdrawing group selected from the group consisting of halogen, CF 3 , CN, C(O)R, CO 2 R, NO 2 , and SO 2 R; and

wherein each R is independently selected from the group consisting of hydrogen, deuterium, halogen, pseudohalogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, amide, hydroxyl, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, heteroalkynyl, aryl, heteroaryl, nitro, nitrile, isonitrile, sulfanyl, boryl, acyl, carboxylic acid, benzoyl, ether, ester, vinyl, ketone, sulfinyl, sulfonyl, cyano, phosphino, and combinations thereof; wherein any two adjacent substituents may together join to form a ring.

10 . The compound of claim 1 , wherein L is represented by one of the following structures:

wherein each R is independently selected from the group consisting of hydrogen, deuterium, halogen, pseudohalogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, amide, hydroxyl, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, heteroalkynyl, aryl, heteroaryl, nitro, nitrile, isonitrile, sulfanyl, boryl, acyl, carboxylic acid, benzoyl, ether, ester, vinyl, ketone, sulfinyl, sulfonyl, cyano, phosphino, and combinations thereof; wherein any two adjacent substituents may together join to form a ring.

11 . The compound of claim 1 , wherein Z is selected from the group consisting of an alkyl anion, aryl anion, heteroaryl anion, halide, trifluoromethylsulfonate, amide, alkoxide, sulfide, and phosphide, wherein Z may be further substituted.

12 . The compound of claim 1 , wherein Z is represented by one of the following structures:

wherein the dashed line indicates the bond to M 1 ; and

each occurrence Y is selected from the group consisting of N and CR; and

each R independently represents a substituent selected from the group consisting of hydrogen, deuterium, halogen, pseudohalogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, amide, hydroxyl, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, heteroalkynyl, aryl, heteroaryl, nitro, nitrile, isonitrile, sulfanyl, boryl, acyl, carboxylic acid, benzoyl, ether, ester, vinyl, ketone, sulfinyl, sulfonyl, cyano, phosphino, and combinations thereof; wherein any two adjacent substituents may together join to form a ring.

13 . The compound of claim 1 , wherein Z is represented by one of the following structures:

wherein the dashed line indicates the bond to M 1 .

14 . The compound of claim 1 , wherein the compound is represented by one of the following structures

wherein dipp represents 2,6-diisopropylphenyl.

15 . An organic electroluminescent device comprising:

an anode;

a cathode; and

an organic layer, disposed between the anode and the cathode, comprising a compound represented by the following Formula I:

wherein is selected from the group consisting of Au(I), Ag(I), and Cu(I);

L is a carbene coordinated to the metal M 1 ;

Z is a monoanionic ligand;

E 1 is an electron accepting group;

n is an integer from 1 to the maximum allowable substitution on L, wherein when n is greater than 1, each E 1 may be the same or different;

E 1 , L, and Z may each be substituted with one or more substituents independently selected from the group consisting of hydrogen, deuterium, halogen, pseudohalogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, amide, hydroxyl, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, heteroalkynyl, aryl, heteroaryl, nitro, nitrile, isonitrile, sulfanyl, boryl, acyl, carboxylic acid, benzoyl, ether, ester, vinyl, ketone, sulfinyl, sulfonyl, cyano, phosphino, and combinations thereof; wherein any two adjacent substituents may together join to form a ring.

16 . The organic electroluminescent device of claim 15 , wherein the organic layer is an emissive layer and the compound is an emissive dopant or a non-emissive dopant.

17 . The organic electroluminescent device of claim 15 , wherein the organic layer further comprises a host, wherein the host comprises at least one chemical group selected from the group consisting of triphenylene, carbazole, dibenzothiphene, dibenzofuran, dibenzoselenophene, azatriphenylene, azacarbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene.

18 . A consumer product comprising an organic light-emitting device (OLED) comprising:

an anode;

a cathode; and

an organic layer, disposed between the anode and the cathode, comprising a compound represented by the following Formula I:

wherein is selected from the group consisting of Au(I), Ag(I), and Cu(I);

L is a carbene coordinated to the metal M 1 ;

Z is a monoanionic ligand;

E 1 is an electron accepting group;

n is an integer from 1 to the maximum allowable substitution on L, wherein when n is greater than 1, each E 1 may be the same or different;

E 1 , L, and Z may each be substituted with one or more substituents independently selected from the group consisting of hydrogen, deuterium, halogen, pseudohalogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, amide, hydroxyl, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, heteroalkynyl, aryl, heteroaryl, nitro, nitrile, isonitrile, sulfanyl, boryl, acyl, carboxylic acid, benzoyl, ether, ester, vinyl, ketone, sulfinyl, sulfonyl, cyano, phosphino, and combinations thereof; wherein any two adjacent substituents may together join to form a ring.

19 . The consumer product of claim 18 , wherein the consumer product is selected from the group consisting of a flat panel display, a computer monitor, a medical monitors television, a billboard, a light for interior or exterior illumination and/or signaling, a heads-up display, a fully or partially transparent display, a flexible display, a laser printer, a telephone, a cell phone, tablet, a phablet, a personal digital assistant (PDA), a wearable device, a laptop computer, a digital camera, a camcorder, a viewfinder, a micro-display, a 3-D display, a virtual reality or augmented reality display, a vehicle, a large area wall, a theater or stadium screen, and a sign.

20 . A formulation comprising the compound of claim 1 .

Assignments (2)

Continuity (3)

References Cited (207)