# US 12,120,946 B2 · Green and red organic light-emitting diodes employing excimer emitters

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- Number: US 12,120,946 B2
- Document ID: US12120946B2
- Status: Granted
- Kind: B2
- Application number: 18/467,348
- Filed: 2023-09-14
- Published: 2024-01-11
- Granted: 2024-10-15
- Earliest claimed: 2019-10-02
- Assignees: Arizona Board of Regents on behalf of Arizona State University
- Applicants: Arizona Board of Regents on behalf of Arizona State University
- Inventors: Jian Li; Jiang Wu
- Web page: https://patentgrep.com/patent/US12120946B2

## CPC

- H10K 85/341: {Transition metal complexes, e.g. Ru(II)polypyridine complexes (H10K85/331 takes precedence)}
- C09K 11/06: containing organic luminescent materials
- H10K 85/342: {comprising iridium}
- H10K 85/346: {comprising platinum}
- H10K 85/371: {Metal complexes comprising a group IB metal element, e.g. comprising copper, gold or silver}
- C09K 2211/1029: containing one nitrogen atom as the heteroatom
- C09K 2211/1044: containing two nitrogen atoms as heteroatoms
- C09K 2211/185: of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
- H10K 50/11: characterised by the electroluminescent [EL] layers
- H10K 50/125: specially adapted for multicolour light emission, e.g. for emitting white light
- H10K 2101/10: Triplet emission
- H10K: ORGANIC ELECTRIC SOLID-STATE DEVICES
- C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE

## Abstract

Organic light emitting devices (OLEDs) are described, the OLEDs comprising an anode; a cathode; and an organic region, disposed between the anode and the cathode, comprising a first complex and a second complex; wherein when a voltage is applied across the anode and cathode at room temperature, the OLED emits a luminescent radiation that comprises one or more luminescent radiation components resulting from the formation of at least one exciplex; wherein the exciplex is formed by at least one of the following aggregate types: 1) at least one aggregate within the first complex, and at least one aggregate within the second complex; 2) at least one aggregate between the first and the second complex; and 3) both 1 and 2.

## Claims

### Claim 1

A composition comprising a first complex and a second complex, wherein the first complex and the second complex each have a structure independently selected from General Formula I and General Formula II;
wherein:
M represents Pt(II), Pd(II), Ir(I), Rh(I), Au(III);
Y1a, Y1b, y1e, Y1f, y1g, Y1h, Y2a, Y2b, Y2c, Y2f, Y2g, Y2h each independently represents C or N;
Y1d, Y1e, Y2d, Y2e each is independently absent or present, and if present, Y1d, Y1e, Y2d, Y2e each independently represents C or N;
X and X1 each is independently present or absent, and each of X and X1, if present, independently represents C, N, Si, O, S, Ge, P, As, Se, B, Al, or Bi, or if valency permits, each independently represents CR7, SiR7, GeR7, NR7, P═O, As═O, B, BR7, AlR7, Bi═O, CR7R8, C═O, SiR7R8, GeR7R8, PR7, PR7R8, R7P═O, AsR7, R7As═O, S═O, SO2, Se═O, SeO2, BR7R8, AlR7R8, R7Bi═O, or BiR7;
R1, R2, R3, R4, R5, R6, R7, and R8 each is independently absent or present as a single substituent or multiple substituents, valency permitting, and, if present, each of R1, R2, R3, R4, R5, R6, R7, and R8 independently represents hydrogen, deuterium, halogen, hydroxyl, thiol, nitro, cyano, nitrile, isonitrile, sulfinyl, mercapto, sulfo, carboxyl, hydrazino; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, ureido, phosphoramide, silyl, polymeric; or any conjugate or combination thereof;
L1, L3, L4, and L6 each independently represents a 5- to 10-membered aryl, heteroaryl, fused aryl, or fused heteroaryl;
L2 and L5 each is independently present or absent and, if present, L2 and L5 each independently represents a 5- to 10-membered aryl, heteroaryl, fused aryl, or fused heteroaryl;
V1, V2, V3, V4 each is independently present, absent, or a covalent bond, and, if present, each of V1, V2, V3, V4 independently represents C, N, Si, O, S, Ge, P, As, Se, B, Al, or Bi, or if valency permits, each independently represents CR7, SiR7, GeR7, NR7, P═O, As═O, B, BR7, AlR7, Bi═O, CR7R8, C═O, SiR7R8, GeR7R8, PR7, PR7R8, R7P═O, AsR7, R7As═O, S═O, SO2, Se═O, SeO2, BR7R8, AlR7R8, R7Bi═O, or BiR7;
each n is independently an integer, valency permitting; and
wherein the first complex and the second complex have different structures.

### Claim 2 (depends on 1)

The composition of claim 1, wherein, in at least one of the first complex and the second complex, at least one of R1, R2, R3, R4, R5, or R6 in any of General Formula I or General Formula II is a C1-C6 linear alkyl group or a C3-C6 branched alkyl group.

### Claim 3 (depends on 1)

The composition of claim 1, wherein, in at least one of the first complex and the second complex, at least one of R1, R2, R3, R4, R5, or R6 in any of General Formula I or General Formula II is selected from the group consisting of: a methyl group, an ethyl group, an iso-propyl group, and a tert-butyl group.

### Claim 4 (depends on 1)

The composition of claim 1, wherein, in at least one of the first complex and the second complex, at least one of R1, R2, R3, R4, R5, or R6 in any of General Formula I or General Formula II is an optionally substituted C6-C24 aryl group.

### Claim 5 (depends on 1)

The composition of claim 1, wherein, in at least one of the first complex and the second complex, at least one of R1, R2, R3, R4, R5, or R6 in any of General Formula I or General Formula II is selected from the group consisting of:

### Claim 6 (depends on 1)

The composition of claim 1, wherein, in at least one of the first complex and the second complex, at least one of R1, R2, R3, R4, R5, or R6 in any of General Formula I or General Formula II is selected from the group consisting of:
wherein R and R9 each independently represents hydrogen, deuterium, halogen, hydroxyl, thiol, nitro, cyano, nitrile, isonitrile, sulfinyl, mercapto, sulfo, carboxyl, hydrazino; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, ureido, phosphoramide, silyl, polymeric; or any conjugate or combination thereof.

### Claim 7 (depends on 1)

The composition of claim 1, wherein at least one of V3, V4, or X1 is present in General Formula I or General Formula II.

### Claim 8 (depends on 1)

The composition of claim 1, wherein M in one of the first complex and the second complex is Pt(II); and M in the other of the first complex and the second complex is Pd(II).

### Claim 9 (depends on 1)

The composition of claim 1, wherein the first complex and the second complex each have a structure of General Formula I.

### Claim 10 (depends on 1)

The composition of claim 1, wherein at least one of the first complex and the second complex is a complex of General Formula III, General Formula IV, General Formula V, or General Formula VI;
wherein, in General Formulas III-VI:
M represents Pt(II), Pd(II), Ir(I), Rh(I), or Au(III);
each Y1a, Y1b, Y1e, Y1d, Y2a, Y2b, Y2c, Y2d, Y2e, Y2f, Y3a, Y3b, Z1, Z2, Z3, and Z4 independently represents C or N;
X and X1 each is independently present or absent, and, if present, each of X and X1 independently represents C, N, Si, O, S, Ge, P, As, Se, B, Al, or Bi, or if valency permits, each independently represents CR7, SiR7, GeR7, NR7, P═O, As═O, B, BR7, AlR7, Bi═O, CR7R8, C═O, SiR7R8, GeR7R8, PR7, PR7R8, R7P═O, AsR7, R7As═O, S═O, SO2, Se═O, SeO2, BR7R8, AlR7R8, R7Bi═O, or BiR7;
A, B, C, and D each independently represents C, N, O, or S;
R1, R2, R3, R4, R5, R6, R7, and R8 each is independently absent or present as a single substituent or multiple substituents, valency permitting, and, if present, each of R1, R2, R3, R4, R5, R6, R7, and R8 independently represents hydrogen, deuterium, halogen, hydroxyl, thiol, nitro, cyano, nitrile, isonitrile, sulfinyl, mercapto, sulfo, carboxyl, hydrazino; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, ureido, phosphoramide, silyl, polymeric; or any conjugate or combination thereof;
L4, L5, and L6 each independently represents a 5- to 10-membered aryl, heteroaryl, fused aryl, or fused heteroaryl;
V1 and V2 each is independently present, absent, or a covalent bond, and if present, each of V1 and V2 independently represents C, N, Si, O, S, Ge, P, As, Se, B, Al, or Bi, or if valency permits, each independently represents CR7, SiR7, GeR7, NR7, P═O, As═O, B, BR7, Bi═O, CR7R8, C═O, SiR7R8, GeR7R8, PR7, PR7R8, R7P═O, AsR7, R7As═O, S═O, SO2, Se═O, SeO2, BR7R8, AlR7, AlR7R8, R7Bi═O, or BiR7; and
each n is independently an integer, valency permitting.

### Claim 11 (depends on 1)

The composition of claim 1, wherein one of the first complex and the second complex has a structure of General Formula III, and the other of the first complex and the second complex has a structure of General Formula IV.

### Claim 12 (depends on 1)

The composition of claim 1, wherein at least one of the first complex and the second complex is a complex of General Formula VII, General Formula VIII, General Formula IX, General Formula X, General Formula XI, General Formula XII, General Formula XIII, General Formula XIV, General Formula XV, General Formula XVI, General Formula XVII, General Formula XVIII, General Formula XIX, General Formula XX, General Formula XXI, General Formula XXII, General Formula XXIII, or General Formula XXIV:
wherein, in General Formulas VII-XXIV:
Y1a, Y1b, Y1c, Y1d, Y1e, Y1f, Y1g, Y1h, Y1i, Y1j, Y2a, Y2b, Y2c, Y2d Y2e, Y2f, Y2g, Y2h, Y2i Y2j each independently represents C or N;
X is independently present or absent, and, if present, X independently represents C, N, Si, O, S, Ge, P, As, Se, B, Al, or Bi, or if valency permits, X independently represents CR7, SiR7, GeR7, NR7, P═O, As═O, B, BR7, AlR7, Bi═O, CR7R8, C═O, SiR7R8, GeR7R8, PR7, PR7R8, R7P═O, AsR7, R7As═O, S═O, SO2, Se═O, SeO2, BR7R8, AlR7R8, R7Bi═O, or BiR7;
A, B, C, D, A1, B1, C1, and D1 each independently represents C, N, O, S;
R1, R2, R3, R4, R5, R6, R7, and R8 is each independently absent or present as a single substituent or multiple substituents, valency permitting, and, if present, each of R1, R2, R3, R4, R5, R6, R7, and R8 independently represents hydrogen, deuterium, halogen, hydroxyl, thiol, nitro, cyano, nitrile, isonitrile, sulfinyl, mercapto, sulfo, carboxyl, hydrazino; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, ureido, phosphoramide, silyl, polymeric; or any conjugate or combination thereof; and
each n is independently an integer, valency permitting.

### Claim 13 (depends on 1)

The composition of claim 1, wherein at least one of the first complex and the second complex has a structure of General Formula VIII.

### Claim 14 (depends on 1)

The composition of claim 1, wherein at least one of the first complex and the second complex is a complex of General Formula XXV, General Formula XXVI, General Formula XXVII, General Formula XXVIII, General Formula XXIX, General Formula XXX, General Formula XXXI, or General Formula XXXII;
wherein, in General Formulas XXV-XXXII:
Y1a, Y1b, Y1c, Y1d, y1e, Y1f, y1g, Y1h, Y1i, Y1j, Y2a, Y2b, Y2c, Y2d Y2e, Y2f, Y2g, Y2h, Y2i, Y2j each independently represents C or N;
X is independently present or absent, and, if present, X independently represents C, N, Si, O, S, Ge, P, As, Se, B, Al, or Bi, or if valency permits, X independently represents CR7, SiR7, GeR7, NR7, P═O, As═O, B, BR7, AlR7, Bi═O, CR7R8, C═O, SiR7R8, GeR7R8, PR7, PR7R8, R7P═O, AsR7, R7As═O, S═O, SO2, Se═O, SeO2, BR7R8, AlR7R8, R7Bi═O, or BiR7;
A, B, C, D each independently represents C, N, O, S;
R1, R2, R3, R4, R5, R6, R7, and R8 is each independently absent or present as a single substituent or multiple substituents, valency permitting, and, if present, each of R1, R2, R3, R4, R5, R6, R7, and R8 independently represents hydrogen, deuterium, halogen, hydroxyl, thiol, nitro, cyano, nitrile, isonitrile, sulfinyl, mercapto, sulfo, carboxyl, hydrazino; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, ureido, phosphoramide, silyl, polymeric; or any conjugate or combination thereof; and
each n is independently an integer, valency permitting.

### Claim 15 (depends on 1)

The composition of claim 1, wherein at least one of the first complex and the second complex is a complex of General Formula XXXIII, General Formula XXXIV, or General Formula XXXV:
wherein, in General Formulas XXXIII-XXXV:
Y1a, Y1b, Y1e, Y1d, Y1e, Y1f, Y1g, Y1h, Y1i, Y2a, Y2b, Y2c, Y2d Y2e, Y2f, Y2g, Y2h, Y2i, each independently represents C or N;
X is independently present or absent, and, if present, X independently represents C, N, Si, O, S, Ge, P, As, Se, B, Al, or Bi, or if valency permits, each X independently represents CR7, SiR7, GeR7, NR7, P═O, As═O, B, BR7, AlR7, Bi═O, CR7R8, C═O, SiR7R8, GeR7R8, PR7, PR7R8, R7P═O, AsR7, R7As═O, S═O, SO2, Se═O, SeO2, BR7R8, AlR7R8, R7Bi═O, or BiR7;
R1, R2, R3, R4, R5, R6, R7, and R8 is each independently absent or present as a single substituent or multiple substituents, valency permitting, and, if present, each of R1, R2, R3, R4, R5, R6, R7, and R8 independently represents hydrogen, deuterium, halogen, hydroxyl, thiol, nitro, cyano, nitrile, isonitrile, sulfinyl, mercapto, sulfo, carboxyl, hydrazino; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, ureido, phosphoramide, silyl, polymeric; or any conjugate or combination thereof; and
each n is independently an integer, valency permitting.

### Claim 16 (depends on 1)

The composition of claim 1, wherein at least one of the first complex and the second complex is selected from the group consisting of:

### Claim 17 (depends on 1)

The composition of claim 1, wherein the ratio of the first complex to the second complex is any ratio between about 99:1 and about 1:99.

### Claim 18

An organic light emitting device (OLED) comprising:
an anode;
a cathode; and
an organic region, disposed between the anode and the cathode, comprising a first complex and a second complex, wherein the first complex and the second complex each have a structure independently selected from General Formula I and General Formula II;
wherein:
M represents Pt(II), Pd(II), Ir(I), Rh(I), Au(III);
Y1a, Y1b, Y1e, Y1f, Y1g, Y1h, Y2a, Y2b, Y2c, Y2f, Y2g, Y2h each independently represents C or N;
Y1d, Y1e, Y2d, Y2e each is independently absent or present, and if present, Y1d, Y1e, Y2d, Y2e each independently represents C or N;
X and X1 each is independently present or absent, and each of X and X1, if present, independently represents C, N, Si, O, S, Ge, P, As, Se, B, Al, or Bi, or if valency permits, each independently represents CR7, SiR7, GeR7, NR7, P═O, As═O, B, BR7, AlR7, Bi═O, CR7R8, C═O, SiR7R8, GeR7R8, PR7, PR7R8, R7P═O, AsR7, R7As═O, S═O, SO2, Se═O, SeO2, BR7R8, AlR7R8, R7Bi═O, or BiR7;
R1, R2, R3, R4, R5, R6, R7, and R8 each is independently absent or present as a single substituent or multiple substituents, valency permitting, and, if present, each of R1, R2, R3, R4, R5, R6, R7, and R8 independently represents hydrogen, deuterium, halogen, hydroxyl, thiol, nitro, cyano, nitrile, isonitrile, sulfinyl, mercapto, sulfo, carboxyl, hydrazino; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, ureido, phosphoramide, silyl, polymeric; or any conjugate or combination thereof;
L1, L3, L4, and L6 each independently represents a 5- to 10-membered aryl, heteroaryl, fused aryl, or fused heteroaryl;
L2 and L5 each is independently present or absent and, if present, L2 and L5 each independently represents a 5- to 10-membered aryl, heteroaryl, fused aryl, or fused heteroaryl;
V1, V2, V3, V4 each is independently present, absent, or a covalent bond, and, if present, each of V1, V2, V3, V4 independently represents C, N, Si, O, S, Ge, P, As, Se, B, Al, or Bi, or if valency permits, each independently represents CR7, SiR7, GeR7, NR7, P═O, As═O, B, BR7, AlR7, Bi═O, CR7R8, C═O, SiR7R8, GeR7R8, PR7, PR7R8, R7P═O, AsR7, R7As═O, S═O, SO2, Se═O, SeO2, BR7R8, AlR7R8, R7Bi═O, or BiR7;
each n is independently an integer, valency permitting; and
wherein the first complex and the second complex have different structures.

### Claim 19

A consumer product comprising an organic light emitting device (OLED) comprising:
an anode;
a cathode; and
an organic region, disposed between the anode and the cathode, comprising a first complex and a second complex, wherein the first complex and the second complex each have a structure independently selected from General Formula I and General Formula II;
wherein:
M represents Pt(II), Pd(II), Ir(I), Rh(I), Au(III);
Y1a, Y1b, Y1e, Y1f, Y1g, Y1h, Y2a, Y2b, Y2c, Y2f, Y2g, Y2h each independently represents C or N;
Y1d, Y1e, Y2d, Y2e each is independently absent or present, and if present, Y1d, Y1e, Y2d Y2e each independently represents C or N;
X and X1 each is independently present or absent, and each of X and X1, if present, independently represents C, N, Si, O, S, Ge, P, As, Se, B, Al, or Bi, or if valency permits, each independently represents CR7, SiR7, GeR7, NR7, P═O, As═O, B, BR7, AlR7, Bi═O, CR7R8, C═O, SiR7R8, GeR7R8, PR7, PR7R8, R7P═O, AsR7, R7As═O, S═O, SO2, Se═O, SeO2, BR7R8, AlR7R8, R7Bi═O, or BiR7;
R1, R2, R3, R4, R5, R6, R7, and R8 each is independently absent or present as a single substituent or multiple substituents, valency permitting, and, if present, each of R1, R2, R3, R4, R5, R6, R7, and R8 independently represents hydrogen, deuterium, halogen, hydroxyl, thiol, nitro, cyano, nitrile, isonitrile, sulfinyl, mercapto, sulfo, carboxyl, hydrazino; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, ureido, phosphoramide, silyl, polymeric; or any conjugate or combination thereof;
L1, L3, L4, and L6 each independently represents a 5- to 10-membered aryl, heteroaryl, fused aryl, or fused heteroaryl;
L2 and L5 each is independently present or absent and, if present, L2 and L5 each independently represents a 5- to 10-membered aryl, heteroaryl, fused aryl, or fused heteroaryl;
V1, V2, V3, V4 each is independently present, absent, or a covalent bond, and, if present, each of V1, V2, V3, V4 independently represents C, N, Si, O, S, Ge, P, As, Se, B, Al, or Bi, or if valency permits, each independently represents CR7, SiR7, GeR7, NR7, P═O, As═O, B, BR7, AlR7, Bi═O, CR7R8, C═O, SiR7R8, GeR7R8, PR7, PR7R8, R7P═O, AsR7, R7As═O, S═O, SO2, Se═O, SeO2, BR7R8, AlR7R8, R7Bi═O, or BiR7;
each n is independently an integer, valency permitting; and
wherein the first complex and the second complex have different structures.

### Claim 20 (depends on 19)

The consumer product of claim 19, 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, and a sign.