# US 9,520,574 B2 · Electroluminescent devices based on phosphorescent iridium and related group VIII metal multicyclic compounds

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 9,520,574 B2
- Document ID: US9520574B2
- Status: Granted
- Kind: B2
- Application number: 13/643,054
- Filed: 2011-04-28
- Published: 2013-04-04
- Granted: 2016-12-13
- Earliest claimed: 2010-04-28
- Assignees: Commonwealth Scientific and Industrial Research Organisation
- Applicants: Michelle Groarke; Kazunori Ueno; Mark Bown; Sven Andresen
- Inventors: Michelle Groarke; Kazunori Ueno; Mark Bown; Sven Andresen
- Web page: https://patentgrep.com/patent/US9520574B2

## CPC

- H10K 50/11: characterised by the electroluminescent [EL] layers
- C07F 15/0033: {Iridium compounds}
- C09K 11/06: containing organic luminescent materials
- H05B 33/10: Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
- H10K 85/342: {comprising iridium}
- C09K 2211/1007: Non-condensed systems
- C09K 2211/1011: Condensed systems
- C09K 2211/1029: containing one nitrogen atom as the heteroatom
- C09K 2211/1037: with sulfur
- C09K 2211/1044: containing two nitrogen atoms as heteroatoms
- C09K 2211/1059: containing three nitrogen atoms as heteroatoms
- C09K 2211/185: of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
- H10K 2101/10: Triplet emission
- H10K: ORGANIC ELECTRIC SOLID-STATE DEVICES
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- H05B: ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL

## Abstract

Disclosed herein are phosphorescent materials comprising a complex of a metal atom M selected from Ir, Pt, Rh, Pd, Ru and Os and at least one ligand L, wherein the ligand L is represented by formula (1). Also disclosed are organic electroluminescent devices including such phosphorescent materials.

## Claims

### Claim 1

An organic electroluminescent device comprising:
a pair of electrodes comprising an anode and a cathode, and
one or more layers of organic compound arranged between the anode and the cathode, wherein at least one of the one or more layers of organic compound comprises a phosphorescent material; wherein the phosphorescent material comprises a complex of a metal atom M selected from Ir, Pt, Rh, Pd, Ru and Os and at least one ligand L, wherein the ligand L is represented by formula (1):
wherein:
ring A is a substituted or unsubstituted 5-membered heterocycle containing at least one ring nitrogen atom bound to the metal atom at the asterisk (*), wherein ring A may be substituted with one or more substituents selected from the group consisting of:
halogen, cyano, amide, imine, imide, amidine, amine, nitro, hydroxy, ether, carbonyl, carboxy, carbonate, carbamate, phosphine, phosphate, phosphonate, sulphide, sulphone, sulphoxide, silyl, substituents containing a functional group that can be polymerised or a polymer chain, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, and substituted or unsubstituted alkynyl, wherein:
one or more of the carbon atoms in the alkyl may be replaced, wherein each carbon atom that is replaced is independently replaced with an atom or group selected from the group consisting of: —C(═O)—, —O—, —S—, —N', —C═N—, —Si— and —P—;
ring B is a substituted or unsubstituted 5- or 6-membered carbocycle or heterocycle containing a carbon atom as represented in formula (1) which is bound to the metal atom at the asterisk (*),
rings A and B are joined by a direct covalent bond as represented in formula (1),
rings A and B are joined via a tether Q, wherein
Q is a tether of between 3 and 20 atoms in length, and is selected from the group consisting of: linear, branched or cyclic alkyl; linear or branched alkenyl; linear or branched alkynyl; aryl; and alkyl-aryl; wherein one or more of the carbon atoms in the alkyl, aryl or alkyl-aryl may be replaced, wherein each carbon atom that is replaced is independently replaced with an atom or group selected from the group consisting of: —C(═O)—, —O—, —S—, —N—, ═N—, —Si— and —P—; wherein when the atom is ═N—, the nitrogen double bond is to an adjacent carbon atom in the alkyl, aryl, or alkyl-aryl so as to form a —C═N— group; and wherein the tether may contain one or more substituents selected from the group consisting of halogen, cyano, amide, imine, imide, amidine, amine, nitro, hydroxy, ether, carbonyl, carboxy, carbonate, carbamate, phosphine, phosphate, phosphonate, sulphide, sulphone, sulphoxide, alkenyl, aryl, alkyl, heteroaryl, alkynyl, silyl, and substituents containing a functional group that can be polymerised, a polymer chain, or two substituents may together form a ring or fused ring system.

### Claim 2 (depends on 1)

The device of claim 1, wherein ring B may be substituted with one or more substituents selected from the group consisting of:
halogen, cyano, amide, imine, imide, amidine, amine, nitro, hydroxy, ether, carbonyl, carboxy, carbonate, carbamate, phosphine, phosphate, phosphonate, sulphide, sulphone, sulphoxide, silyl, substituents containing a functional group that can be polymerised or a polymer chain, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aryl and substituted or unsubstituted alkyl-aryl, wherein:
one or more of the carbon atoms in the alkyl, aryl or alkyl-aryl may be replaced wherein each carbon atom that is replaced is independently replaced with an atom or group selected from the group consisting of: —C(═O)—, —O—, —S—, —N—, —C═N—, —Si— and —P—,
the substituents on the alkyl, aryl or alkyl-aryl are selected from the group consisting of: halogen, cyano, amide, imine, imide, amidine, amine, nitro, hydroxy, ether, carbonyl, carboxy, carbonate, carbamate, phosphine, phosphate, phosphonate, sulphide, sulphone, sulphoxide, alkenyl, alkynyl, silyl, and substituents containing a functional group that can be polymerised or a polymer chain, and
the alkyl, aryl or alkyl-aryl may additionally be connected to the tether Q, or the alkyl, aryl or alkyl-aryl may be attached via two points to its core ring B to form a fused ring or ring system.

### Claim 3 (depends on 1)

The device of claim 1, wherein the phosphorescent material comprises 1, 2 or 3 ligands L of formula (1), and 0, 1 or 2 bidentate ligands L′ of a different identity to ligand L.

### Claim 4 (depends on 3)

The device of claim 3, wherein the ligand L′ of the phosphorescent material is a ligand of formula (5), a ligand of formula (6) or a ligand of formula (7):
wherein:
ring Y is a 5-, 6- or 7-membered heterocycle which is unsubstituted or substituted by one or more substituents, containing at least one nitrogen atom as represented in the formula, which is bound to the metal atom at the asterisk (*),
ring Y′ is a 5-, 6- or 7-membered heterocycle which is unsubstituted or substituted by one or more substituents, and containing at least one nitrogen atom as represented in the formula which is bound to the metal atom at the asterisk (*), and
rings Y and Y′ are either joined by a direct covalent bond or via a linker J as represented in formula (5), wherein J, when present, is a B, C, O, N, P, Si or S atom which is covalently bonded to both rings Y and Y′ and which may be substituted or unsubstituted depending on its valency;
wherein:
ring Y is as defined in formula (5),
Z is a ligand component connected via a covalent bond to ring Y, and connected to the metal atom via X, and
X is an N, O, S or P atom bound to the metal atom at the asterisk (*), wherein the N or P atom is unsubstituted or is substituted
wherein
G is a ligand component consisting of one or two substituted or unsubstituted carbon atoms in length, which is connected covalently to two O atoms, and
the O atoms are each bound to the metal atom at the asterisk (*).

### Claim 5 (depends on 1)

The device of claim 1, wherein ligand L of the phosphorescent material is of the formula (3):
wherein:
A1 and A2 are each independently selected from the group consisting of: C, N, O and S, wherein the C or N may be substituted or unsubstituted,
A3 and A4 are selected from the group consisting of: C and N, wherein the C may be substituted or unsubstituted.

### Claim 6 (depends on 5)

The device of claim 5, wherein the ligand L of the phosphorescent material is of the formula (4):
wherein:
B1 and B2 are each independently selected from the group consisting of: C, N, O and S, wherein the C or N may be substituted or unsubstituted,
B3, when present, is selected from the group consisting of: C, N, O and S, wherein the C or N may be substituted or unsubstituted,
b is 0 or 1,
B4 is selected from the group consisting of: C and N, wherein the C may be substituted or unsubstituted, and
B5 is C.

### Claim 7 (depends on 6)

The device of claim 6, wherein the ligand L of the phosphorescent material is selected from the group consisting of:
wherein:
R1 and R2 are independently selected from the group consisting of:
hydrogen, halogen, cyano, amide, imine, imide, amidine, amine, nitro, hydroxy, ether, carbonyl, carboxy, carbonate, carbamate, phosphine, phosphate, phosphonate, sulphide, sulphone, sulphoxide, silyl, substituents containing a functional group that can be polymerised or a polymer chain, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, and substituted or unsubstituted alkynyl wherein:
one or more of the carbon atoms in the alkyl may be replaced, wherein each carbon atom that is replaced is independently replaced with an atom or group selected from the group consisting of: —C(═O)—, —O—, —S—, —N—, —C═N—, —Si— and —P—;
the substituents on the alkyl are selected from the group consisting of: halogen, cyano, amide, imine, imide, amidine, amine, nitro, hydroxy, ether, carbonyl, carboxy, carbonate, carbamate, phosphine, phosphate, phosphonate, sulphide, sulphone, sulphoxide, alkenyl, alkynyl, silyl, and substituents containing a functional group that can be polymerised or a polymer chain;
R3, R4, and R5 are independently selected from the group consisting of:
hydrogen, halogen, cyano, amide, imine, imide, amidine, amine, nitro, hydroxy, ether, carbonyl, carboxy, carbonate, carbamate, phosphine, phosphate, phosphonate, sulphide, sulphone, sulphoxide, silyl, and substituents containing a functional group that can be polymerised or a polymer chain, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aryl and substituted or unsubstituted alkyl-aryl, wherein:
one or more of the carbon atoms in the alkyl, aryl or alkyl-aryl may be replaced, wherein each carbon atom that is replaced is independently replaced with an atom or group selected from the group consisting of: —C(═O)—, —O—, —S—, —N—, —C═N—, —Si— and —P—;
the substituents on the alkyl, aryl or alkyl-aryl are selected from the group consisting of: halogen, cyano, amide, imine, imide, amidine, amine, nitro, hydroxy, ether, carbonyl, carboxy, carbonate, carbamate, phosphine, phosphate, phosphonate, sulphide, sulphone, sulphoxide, alkenyl, alkynyl, silyl, and substituents containing a functional group that can be polymerised or a polymer chain;
R6, R7, R8, R9 and R10 are independently selected from the group consisting of:
hydrogen, halogen, cyano, amide, imine, imide, amidine, amine, nitro, hydroxy, ether, carbonyl, carboxy, carbonate, carbamate, phosphine, phosphate, phosphonate, sulphide, sulphone, sulphoxide, alkenyl, aryl, alkyl, heteroaryl, alkynyl, silyl, and substituents containing a functional group that can be polymerised, a polymer chain, or two substituents may together form a ring or fused ring system.

### Claim 8 (depends on 1)

The device of claim 1, wherein the phosphorescent material is of formula (2):
MLmL′n (2)
and wherein:
L′ is a bidentate ligand of a different identity to L,
m is an integer selected from 1, 2 and 3, and
n is an integer selected from 0, 1 and 2.

### Claim 9

A phosphorescent material comprising a complex of a metal atom M selected from Ir, Pt, Rh, Pd, Ru and Os and at least one ligand L, wherein the ligand L is represented by formula (1):
wherein:
ring A is a substituted or unsubstituted 5-membered heterocycle containing at least one ring nitrogen atom bound to the metal atom at the asterisk (*); wherein ring A may be substituted with one or more substituents from the group consisting of:
halogen, cyano, amide, imine, imide, amidine, amine, nitro, hydroxy, ether, carbonyl, carboxy, carbonate, carbamate, phosphine, phosphate, phosphonate, sulphide, sulphone, sulphoxide, silyl, substituents containing a functional group that can be polymerised or a polymer chain, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, and substituted or unsubstituted alkynyl wherein:
one or more of the carbon atoms in the alkyl may be replaced, wherein each carbon atom that is replaced is independently replaced with an atom or group selected from the group consisting of: —C(═O)—, —O—, —S—, —N—, —C═N—, —Si— and —P—;
ring B is a substituted or unsubstituted 5- or 6-membered carbocycle or heterocycle containing a carbon atom as represented in formula (1) which is bound to the metal atom at the asterisk (*),
rings A and B are joined by a direct covalent bond as represented in formula (1),
rings A and B are joined via a tether Q, wherein
Q is a tether of between 3 and 30 atoms in length, and is selected from the group consisting of: linear, branched, or cyclic alkyl; linear or branched alkenyl; linear or branched alkynyl; aryl; alkyl-aryl, wherein one or more of the carbon atoms in the alkyl, aryl or alkyl-aryl may be replaced, wherein each carbon atom that is replaced is independently replaced with an atom or group selected from: —C(═O)—, —O—, —S—, —N—, ═N—, —Si— and —P—, wherein when the atom is ═N—, the nitrogen double bond is to an adjacent carbon atom in the alkyl, aryl, or alkyl-aryl so as to form a —C═N— group; and wherein the tether may contain one or more substituents selected from the group consisting of halogen, cyano, amide, imine, imide, amidine, amine, nitro, hydroxy, ether, carbonyl, carboxy, carbonate, carbamate, phosphine, phosphate, phosphonate, sulphide, sulphone, sulphoxide, alkenyl, aryl, alkyl, heteroaryl, alkynyl, silyl, and substituents containing a functional group that can be polymerised, a polymer chain, or two substituents may together form a ring or fused ring system.

### Claim 10 (depends on 9)

The phosphorescent material of claim 9 having the formula
MLmL′n (2)
wherein:
L′ is a bidentate ligand of a different identity to L,
m is an integer selected from 1, 2 and 3, and
n is an integer selected from 0, 1 and 2.

### Claim 11 (depends on 10)

The phosphorescent material of claim 10, wherein m+n=2 or 3.

### Claim 12 (depends on 10)

The phosphorescent material of claim 10, wherein the ligand L′ is a ligand of formula (5), a ligand of formula (6) or a ligand of formula (7):
wherein:
ring Y is a 5-, 6- or 7-membered heterocycle which is unsubstituted or substituted by one or more substituents, containing at least one nitrogen atom as represented in the formula, which is bound to the metal atom at the asterisk (*),
ring Y′ is a 5-, 6- or 7-membered heterocycle which is unsubstituted or substituted by one or more substituents, and containing at least one nitrogen atom as represented in the formula which is bound to the metal atom at the asterisk (*), and
rings Y and Y′ are either joined by a direct covalent bond or via a linker J as represented in formula (5), wherein J, when present, is a B, C, O, N, P, Si or S atom which is covalently bonded to both rings Y and Y′ and which may be substituted or unsubstituted depending on its valency;
wherein:
ring Y is as defined in formula (5),
Z is a ligand component connected via a covalent bond to ring Y, and connected to the metal atom via X, and
X is an N, O, S or P atom bound to the metal M at the asterisk (*), wherein the N or P atom is unsubstituted or is substituted;
wherein:
G is a ligand component consisting of one or two substituted or unsubstituted carbon atoms in length, which is connected covalently to two O atoms, and
the O atoms are each bound to the metal at the asterisk (*).

### Claim 13 (depends on 12)

The phosphorescent material of claim 12, wherein the ligand L of the phosphorescent material is selected from the group consisting of:
wherein:
R1 and R2 are independently selected from the group consisting of:
hydrogen, halogen, cyano, amide, imine, imide, amidine, amine, nitro, hydroxy, ether, carbonyl, carboxy, carbonate, carbamate, phosphine, phosphate, phosphonate, sulphide, sulphone, sulphoxide, silyl, substituents containing a functional group that can be polymerised or a polymer chain, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, and substituted or unsubstituted alkynyl, wherein:
one or more of the carbon atoms in the alkyl may be replaced, wherein each carbon atom that is replaced is independently replaced with an atom or group selected from the group consisting of: —C(═O)—, —O—, —S—, —N—, —C═N—, —Si— and —P—;
the substituents on the alkyl are selected from the group consisting of: halogen, cyano, amide, imine, imide, amidine, amine, nitro, hydroxy, ether, carbonyl, carboxy, carbonate, carbamate, phosphine, phosphate, phosphonate, sulphide, sulphone, sulphoxide, alkenyl, alkynyl, silyl, and substituents containing a functional group that can be polymerised or a polymer chain;
R3, R4, and R5, are independently selected from the group consisting of:
hydrogen, halogen, cyano, amide, imine, imide, amidine, amine, nitro, hydroxy, ether, carbonyl, carboxy, carbonate, carbamate, phosphine, phosphate, phosphonate, sulphide, sulphone, sulphoxide, silyl, substituents containing a functional group that can be polymerised or a polymer chain, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aryl and substituted or unsubstituted alkyl-aryl, wherein:
one or more of the carbon atoms in the alkyl, aryl or alkyl-aryl may be replaced, wherein each carbon atom that is replaced is independently replaced with an atom or group selected from the group consisting of: —C(═O)—, —O—, —S—, —N—, —C═N—, —Si— and —P—, wherein the atoms —Si— and —P— contain substituents based on their valency;
the substituents on the alkyl, aryl or alkyl-aryl are selected from the group consisting of: halogen, cyano, amide, imine, imide, amidine, amine, nitro, hydroxy, ether, carbonyl, carboxy, carbonate, carbamate, phosphine, phosphate, phosphonate, sulphide, sulphone, sulphoxide, alkenyl, alkynyl, silyl and substituents containing a functional group that can be polymerised or a polymer chain;
R6, R7, R8, R9 and R10 are independently selected from the group consisting of:
hydrogen, halogen, cyano, amide, imine, imide, amidine, amine, nitro, hydroxy, ether, carbonyl, carboxy, carbonate, carbamate, phosphine, phosphate, phosphonate, sulphide, sulphone, sulphoxide, alkenyl, aryl, alkyl, heteroaryl, alkynyl, silyl, and substituents containing a functional group that can be polymerised, a polymer chain, or two substituents may together form a ring or fused ring system.

### Claim 14

A method for the production of a phosphorescent material comprising:
reacting a precursor complex of a metal M, with a ligand L, in a ratio suitable to result in a product containing the desired number of ligands L being co-ordinated to the metal M, optionally followed by:
reacting the product with another ligand L′ in a ratio suitable to introduce the desired number of ligands L′ into the product,
wherein:
M is a metal atom selected from Ir, Pt, Rh, Pd, Ru and Os,
L is a ligand represented by formula (1):
wherein:
ring A is a substituted or unsubstituted 5-membered heterocycle containing at least one ring nitrogen atom bound to the metal atom at the asterisk (*); wherein ring A may be substituted with one or more substituent selected from the group consisting of:
halogen, cyano, amide, imine, imide, amidine, amine, nitro, hydroxy, ether, carbonyl, carboxy, carbonate, carbamate, phosphine, phosphate, phosphonate, sulphide, sulphone, sulphoxide, silyl, substituents containing a functional group that can be polymerised or a polymer chain, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, and substituted or unsubstituted alkynyl, wherein:
one or more of the carbon atoms in the alkyl may be replaced wherein each carbon atom that is replaced is independently replaced with an atom selected from the group consisting of: —C(═O)—, —O—, —S—, —N—, —C═N—, —Si— and —P—;
ring B is a substituted or unsubstituted 5- or 6-membered carbocycle or heterocycle containing a carbon atom as represented in formula (1) which can bind to the metal atom at the asterisk (*),
rings A and B are joined by a direct covalent bond as represented in formula (1),
rings A and B are joined via a tether Q, wherein
Q is a tether of between 3 and 20 atoms in length, and is selected from the group consisting of: linear, branched, or cyclic alkyl; linear or branched alkenyl; linear or branched alkynyl; aryl alkyl-aryl; wherein one or more of the carbon atoms in the alkyl, aryl or alkyl-aryl may be replaced, wherein each carbon atom that is replaced is independently replaced with an atom or group selected from: —C(═O), —O—, —S—, —N—, ═N—, —Si— and —P—, wherein when the atom is ═N—, the nitrogen double bond is to an adjacent carbon atom in the alkyl, aryl, or alkyl-aryl so as to form a —C═N— group; and wherein the tether may contain one or more substituents selected from the group consisting of halogen, cyano, amide, imine, imide, amidine, amine, nitro, hydroxy, ether, carbonyl, carboxy, carbonate, carbamate, phosphine, phosphate, phosphonate, sulphide, sulphone, sulphoxide, alkenyl, aryl, alkyl, heteroaryl, alkynyl, silyl, and substituents containing a functional group that can be polymerised, a polymer chain, or two substituents may together form a ring or fused ring system, and
L′ is a bidentate ligand of a different identity to L.

### Claim 15 (depends on 9)

An organic electroluminescent device comprising the phosphorescent material of claim 9.

### Claim 16 (depends on 1)

The organic electroluminescent device of claim 1, wherein ring A may be substituted with a substituted or unsubstituted alkyl; wherein the substituents on the alkyl are selected from the group consisting of: halogen, cyano, amide, imine, imide, amidine, amine, nitro, hydroxy, ether, carbonyl, carboxy, carbonate, carbamate, phosphine, phosphate, phosphonate, sulphide, sulphone, sulphoxide, alkenyl, alkynyl, silyl, and substituents containing a functional group that can be polymerised or a polymer chain.

### Claim 17 (depends on 9)

The phosphorescent material of claim 9, wherein ring A may be substituted with a substituted or unsubstituted alkyl; wherein the substituents on the alkyl are selected from the group consisting of: halogen, cyano, amide, imine, imide, amidine, amine, nitro, hydroxy, ether, carbonyl, carboxy, carbonate, carbamate, phosphine, phosphate, phosphonate, sulphide, sulphone, sulphoxide, alkenyl, alkynyl, silyl, and substituents containing a functional group that can be polymerised or a polymer chain.

### Claim 18 (depends on 14)

The method of claim 14, wherein ring A may be substituted with a substituted or unsubstituted alkyl; wherein the substituents on the alkyl are selected from the group consisting of: halogen, cyano, amide, imine, imide, amidine, amine, nitro, hydroxy, ether, carbonyl, carboxy, carbonate, carbamate, phosphine, phosphate, phosphonate, sulphide, sulphone, sulphoxide, alkenyl, alkynyl, silyl, and substituents containing a functional group that can be polymerised or a polymer chain.

### Claim 19 (depends on 1)

The organic electroluminescent device of claim 1, wherein ligand L is selected from:

### Claim 20 (depends on 9)

The phosphorescent material of claim 9, wherein ligand L is selected from:

### Claim 21 (depends on 14)

The method of claim 14, wherein ligand L is selected from: