# US 12,006,333 B2 · Organic electroluminescent materials and devices comprising imidazole-containing metal complexes

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- Number: US 12,006,333 B2
- Document ID: US12006333B2
- Status: Granted
- Kind: B2
- Application number: 18/178,189
- Filed: 2023-03-03
- Published: 2023-06-29
- Granted: 2024-06-11
- Earliest claimed: 2019-04-30
- Assignees: Universal Display Corporation
- Applicants: Universal Display Corporation
- Inventors: Scott Beers; Woo-Young So; Hsiao-Fan Chen
- Web page: https://patentgrep.com/patent/US12006333B2

## CPC

- C07F 15/0033: {Iridium compounds}
- C07F 7/0816: {said ring comprising Si as a ring atom}
- C07F 15/006: {Palladium compounds}
- C07F 15/0086: {Platinum compounds}
- H10K 85/342: {comprising iridium}
- H10K 85/346: {comprising platinum}
- H10K 85/40: Organosilicon compounds, e.g. TIPS pentacene
- H10K 85/622: {containing four rings, e.g. pyrene}
- H10K 85/654: {comprising only nitrogen as heteroatom (H10K85/652 takes precedence)}
- H10K 85/6572: {comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole}
- H10K 85/6576: {comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene}
- H10K 50/11: characterised by the electroluminescent [EL] layers
- H10K 50/121: {for assisting energy transfer, e.g. sensitization}
- H10K 2101/10: Triplet emission
- H10K 2101/40: Interrelation of parameters between multiple constituent active layers or sublayers, e.g. HOMO values in adjacent layers
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- H10K: ORGANIC ELECTRIC SOLID-STATE DEVICES

## Abstract

A compound comprising a first ligand LA of Formula I or Formula II: wherein A1 and A2 are each independently C or Si; wherein each RA, and RB independently represents mono to the maximum allowable substitution, or no substitution; wherein each X1, X2, and X3 is independently C or N; wherein each R, R1, R2, R3, R4 and RA is independently a hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; wherein LA is complexed to a metal M; wherein M is optionally coordinated to one or more other ligands; wherein the ligand LA is optionally linked with the one or more other ligands to form a tridentate, tetradentate, pentadentate, or hexadentate ligand; and wherein any two substituents are optionally joined or fused together to form a ring.

## Claims

### Claim 1

A compound comprising a first ligand LA of Formula I:
wherein A1 and A2 are each independently C or Si;
wherein each RA independently represents mono to the maximum allowable substitution, or no substitution;
wherein each R, R1, R2, R3, R4 and RA is independently a hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof;
wherein LA is complexed to a metal M;
wherein M is optionally coordinated to one or more other ligands;
wherein the ligand LA is optionally linked with the one or more other ligands to form a tridentate, tetradentate, pentadentate, or hexadentate ligand; and
wherein any two adjacent substituents are optionally joined or fused together to form a ring.

### Claim 2 (depends on 1)

The compound of claim 1, wherein each R, R1, R2, R3, R4 and RA is independently a hydrogen or a substituent selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, and combinations thereof.

### Claim 3 (depends on 1)

The compound of claim 1, wherein A1 and A2 are each C.

### Claim 4 (depends on 1)

The compound of claim 1, wherein R1, R2, R3, and R4 are each independently selected from the group consisting of hydrogen and alkyl.

### Claim 5 (depends on 1)

The compound of claim 1, wherein R is selected from the group consisting of hydrogen, alkyl, and aryl.

### Claim 6 (depends on 1)

The compound of claim 1, wherein M is Pt, Pd, or Jr.

### Claim 7 (depends on 1)

The compound of claim 1, wherein the first ligand LA is selected from the group consisting of:

### Claim 8 (depends on 1)

The compound of claim 1, wherein the first ligand LA is selected from the group consisting of LA1-LA64;
wherein of LA1-LA36 are ligands of Formula III:
wherein A1, A2, R, RA, R1, R2, R3, R4 are defined aS follows:
LA
R
A1
R1
R2
A2
R3
R4
RA
LA1
2,6-di-iPr—Ph
C
CH3
CH3
C
CH3
CH3
H
LA2
2,6-di-iPr—Ph
C
CH3
CH3
C
CH3
CH3
2,6-di-iPr—Ph
LA3
H
C
CH3
CH3
C
CH3
CH3
2,6-di-iPr—Ph
LA4
H
C
CH3
CH3
C
CH3
CH3
H
LA5
H
Si
CH3
CH3
C
CH3
CH3
H
LA6
2,6-di-iPr—Ph
Si
CH3
CH3
C
CH3
CH3
H
LA7
2,6-di-iPr—Ph
Si
isopropyl
isopropyl
C
CH3
CH3
H
LA8
H
Si
CH3
CH3
C
CH3
CH3
H
LA9
H
Si
CH3
CH3
C
CH3
CH3
2,6-di-iPr—Ph
LA10
2,6-di-iPr—Ph
Si
CH3
CH3
C
CH3
CH3
2,6-di-iPr—Ph
LA11
H
Si
isopropyl
isopropyl
C
CH3
CH3
H
LA12
H
Si
CH3
CH3
C
CH3
CH3
2,6-di-iPr—Ph
LA13
H
C
CH3
CH3
Si
CH3
CH3
H
LA14
H
C
CH3
CH3
Si
CH3
CH3
2,6-di-iPr—Ph
LA15
2,6-di-iPr—Ph
C
CH3
CH3
Si
CH3
CH3
2,6-di-iPr—Ph
LA16
2,6-di-iPr—Ph
C
CH3
CH3
Si
CH3
CH3
H
LA17
H
C
CH3
CH3
Si
i-Pr
i-Pr
H
LA18
H
C
CH3
CH3
Si
i-Pr
i-Pr
2,6-di-iPr—Ph
LA19
2,6-di-iPr—Ph
C
CH3
CH3
Si
i-Pr
i-Pr
2,6-di-iPr—Ph
LA20
H
C
CD3
CD3
C
CD3
CD3
H
LA21
H
C
CD3
CD3
C
CD3
CD3
2,6-di-iPr—Ph
LA22
Phenyl
C
CD3
CD3
C
CD3
CD3
H
LA23
H
C
CD3
CD3
C
CD3
CD3
Phenyl
LA24
2,6-di-iPr—Ph
C
CD3
CD3
C
CD3
CD3
H
LA25
H
C
CD3
CD3
C
CD3
CD3
isopropyl
LA26
H
C
CD3
CD3
Si
CH3
CH3
H
LA27
H
C
CD3
CD3
Si
CD3
CD3
H
LA28
Phenyl
C
CH3
CH3
C
CH3
CH3
H
LA29
Phenyl
C
CD3
CD3
Si
CH3
CH3
H
LA30
Phenyl
Si
CH3
CH3
C
CD3
CD3
Phenyl
LA31
H
Si
isopropyl
isopropyl
C
CH3
CH3
Phenyl
LA32
H
C
CD3
CD3
Si
CH3
CH3
t-Butyl
LA33
Phenyl
C
CH3
CH3
C
CH3
CH3
t-Butyl
LA34
Phenyl
C
CD3
CD3
Si
isopropyl
isopropyl
isopropyl
LA35
Phenyl
Si
CD3
CD3
C
CD3
CD3
t-Butyl
LA36
H
Si
CD3
CD3
C
CD3
CD3
t-Butyl
wherein of LA37-LA64 are ligands of Formula IV:
wherein A1, A2, R, RA, R1, R2, R3, and R4 are defined as follows:
LA
R
A1
R1
R2
A2
R3
R4
RA
LA37
H
C
CH3
CH3
C
CH3
CH3
CH3
LA38
Phenyl
C
CH3
CH3
C
CH3
CH3
CH3
LA39
2,6-di-
C
CH3
CH3
C
CH3
CH3
CH3
iPr—Ph
LA40
CD3
C
CH3
CH3
C
CH3
CH3
CH3
LA41
H
C
CD3
CD3
C
CD3
CD3
CD3
LA42
Phenyl
C
CD3
CD3
C
CD3
CD3
CD3
LA43
2,6-di-
C
CD3
CD3
C
CD3
CD3
CD3
iPr—Ph
LA44
CD3
C
CD3
CD3
C
CD3
CD3
CD3
LA45
H
C
CH3
CH3
Si
CH3
CH3
CH3
LA46
Phenyl
C
CH3
CH3
Si
CH3
CH3
CH3
LA47
2,6-di-
C
CH3
CH3
Si
CH3
CH3
CH3
iPr—Ph
LA48
CD3
C
CH3
CH3
Si
CH3
CH3
CH3
LA49
H
C
CD3
CD3
Si
CH3
CH3
CH3
LA50
Phenyl
C
CD3
CD3
Si
CH3
CH3
CH3
LA51
2,6-di-
C
CD3
CD3
Si
CH3
CH3
CH3
iPr—Ph
LA52
CD3
C
CD3
CD3
Si
CH3
CH3
CH3
LA53
H
Si
CH3
CH3
C
CH3
CH3
CH3
LA54
Phenyl
Si
CH3
CH3
C
CH3
CH3
CH3
LA55
2,6-di-
Si
CH3
CH3
C
CH3
CH3
CH3
iPr—Ph
LA56
CD3
Si
CH3
CH3
C
CH3
CH3
CH3
LA57
H
Si
CH3
CH3
C
CD3
CD3
CD3
LA58
Phenyl
Si
CH3
CH3
C
CD3
CD3
CD3
LA59
2,6-di-
Si
CH3
CH3
C
CD3
CD3
CD3
iPr—Ph
LA60
CD3
Si
CH3
CH3
C
CD3
CD3
CD3
LA61
H
Si
isopropyl
isopropyl
C
CH3
CH3
CH3
LA62
Phenyl
Si
isopropyl
isopropyl
C
CH3
CH3
CH3
LA63
2,6-di-
Si
isopropyl
isopropyl
C
CH3
CH3
CH3
iPr—Ph
LA64
CD3
Si
isopropyl
isopropyl
C
CH3
CH3
CH3
and wherein 2,6-di-iPr-Ph is

### Claim 9 (depends on 8)

The compound of claim 8 wherein the compound is the Compound Ax having the formula Ir(LAi)3; or the Compound By having the formula Ir(LAi)(LBk)2;
wherein x=i and y=468i+k−468;
wherein i is an integer from 1 to 64 and k is an integer from 1 to 468;
wherein LBk is selected from the group consisting of the following structures:

### Claim 10 (depends on 1)

The compound of claim 1, wherein the compound has a formula of M(LA)x(LB)y(LC)z wherein LB and LC are each a bidentate ligand; and wherein x is 1, 2, or 3; y is 0, 1, or 2; z is 0, 1, or 2; and x+y+z is the oxidation state of the metal M.

### Claim 11 (depends on 10)

The compound of claim 10, wherein the compound has a formula selected from the group consisting of Ir(LA)3, Ir(LA)(LB)2, Ir(LA)2(LB), Ir(LA)(LB)(LC), wherein LA, LB, and LC are different from each other; or the compound has a formula of Pt(LA)(LB), wherein LA and LB are the same or different.

### Claim 12 (depends on 10)

The compound of claim 10, wherein LB and LC are each independently selected from the group consisting of:
wherein each Y1 to Y13 is independently selected from the group consisting of carbon and nitrogen;
wherein Y′ is selected from the group consisting of BRe, NRe, PRe, O, S, Se, C═O, S═O, SO2, CReRf, SiReRf, and GeReRf;
wherein Re and Rf are optionally fused or joined to form a ring;
wherein each Ra, Rb, Rc, and Rd independently represents from mono substitution to the maximum possible number of substitution, or no substitution;
wherein each Ra, Rb, Rc, Rd, Re and Rf is independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, and
wherein any two adjacent substituents of Ra, Rb, Rc, and Rd are optionally fused or joined to form a ring or form a multidentate ligand.

### Claim 13

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 comprising a first ligand LA of Formula I:
wherein A1 and A2 are each independently C or Si;
wherein each RA independently represents mono to the maximum allowable substitution, or no substitution;
wherein each R, R1, R2, R3, R4 and RA is independently a hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof,
wherein LA is complexed to a metal M;
wherein M is optionally coordinated to one or more other ligands;
wherein the ligand LA is optionally linked with the one or more other ligands to form a tridentate, tetradentate, pentadentate, or hexadentate ligand; and
wherein any two adjacent substituents are optionally joined or fused together to form a ring.

### Claim 14 (depends on 13)

The OLED of claim 13, 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.

### Claim 15 (depends on 14)

The OLED of claim 14, wherein the host is selected from the group consisting of:
and combinations thereof.

### Claim 16

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 comprising a first ligand LA of Formula I:
wherein A1 and A2 are each independently C or Si;
wherein each RA independently represents mono to the maximum allowable substitution, or no substitution;
wherein each R, R1, R2, R3, R4 and RA is independently a hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof,
wherein LA is complexed to a metal M;
wherein M is optionally coordinated to one or more other ligands;
wherein the ligand LA is optionally linked with the one or more other ligands to form a tridentate, tetradentate, pentadentate, or hexadentate ligand; and
wherein any two adjacent substituents are optionally joined or fused together to form a ring.

### Claim 17 (depends on 16)

The consumer product of claim 16, wherein the consumer product is selected from the group consisting of a flat panel display, a computer monitor, a medical monitor, a 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 that is less than 2 inches diagonal, a 3-D display, a virtual reality or augmented reality display, a vehicle, a video wall comprising multiple displays tiled together, a theater or stadium screen, a light therapy device, and a sign.

### Claim 18 (depends on 1)

A formulation comprising a compound of claim 1.