# US 10,118,939 B2 · Metal complexes, comprising carbene ligands having an o-substituted non-cyclometalated aryl group and their use in organic light emitting diodes

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- Number: US 10,118,939 B2
- Document ID: US10118939B2
- Status: Granted
- Kind: B2
- Application number: 15/862,933
- Filed: 2018-01-05
- Published: 2018-05-10
- Granted: 2018-11-06
- Earliest claimed: 2014-03-31
- Assignees: UDC Ireland Limited
- Applicants: Udc Ireland Limited
- Inventors: Stefan Metz; Korinna Dormann; Glauco Battagliarin; Christian Eickhoff; Flavio Luiz Benedito; Soichi Watanabe; Gerhard Wagenblast; Thomas Geßner; Christian Lennartz; Peter Murer
- Web page: https://patentgrep.com/patent/US10118939B2

## CPC

- C07F 15/0033: {Iridium compounds}
- C09B 57/00: Other synthetic dyes of known constitution
- C09B 57/10: Metal complexes of organic compounds not being dyes in uncomplexed form
- C09B 69/008: {Dyes containing a substituent, which contains a silicium atom}
- C09K 11/06: containing organic luminescent materials
- H10K 85/342: {comprising iridium}
- C09K 2211/1007: Non-condensed systems
- C09K 2211/1029: containing one nitrogen atom as the heteroatom
- C09K 2211/1044: containing two nitrogen atoms as heteroatoms
- C09K 2211/1059: containing three nitrogen atoms as heteroatoms
- C09K 2211/1074: containing more than three nitrogen atoms as heteroatoms
- C09K 2211/1088: containing oxygen as the only heteroatom
- 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 85/40: Organosilicon compounds, e.g. TIPS pentacene
- H10K 85/622: {containing four rings, e.g. pyrene}
- H10K 85/6572: {comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole}
- H10K 85/6574: {comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes}
- H10K 2101/10: Triplet emission
- Y02E 10/549: Organic PV cells
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- C09B: ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES {, e.g. PIGMENTS}; MORDANTS; LAKES (fermentation or enzyme using processes to synthesise a desired chemical compound C12P)
- C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- H10K: ORGANIC ELECTRIC SOLID-STATE DEVICES
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

Cyclometallated Ir complex comprising three N,N diaryl substituted carbene ligands, bearing substituents in the 2 position of the non-cyclometallated aryl ring; an organic electronic device, preferably an organic light-emitting diode (OLED), comprising at least one cyclometallated Ir complex as described above, a light-emitting layer comprising said cyclometallated Ir complex preferably as emitter material, preferably in combination with at least one host material, use of said cyclometallated Ir complex in an OLED and an apparatus selected from the group consisting of stationary visual display units, mobile visual display units, illumination units, units in items of clothing, units in handbags, units in accessories, units in furniture and units in wallpaper comprising said organic electronic device, preferably said OLED, or said light-emitting layer. The present invention further relates to a process for the preparation of said cyclometallated Ir complex.

## Claims

### Claim 1

A cyclometallated Ir complex of formula (I)
wherein
A1 is CH or N;
A2 is CR1 or N;
A3 is CR2 or N;
wherein in the case that A1 and/or A3 are N, A2 is CR1;
R1, R2, R3, R4, R6 and R7
are each independently hydrogen; deuterium; a linear or branched, substituted or unsubstituted alkyl radical having from 1 to 20 carbon atoms, optionally interrupted by at least one heteroatom, selected from O, S and N; a substituted or unsubstituted cycloalkyl radical having a total of from 3 to 30 carbon atoms; a substituted or unsubstituted heterocyclo alkyl radical, interrupted by at least one heteroatom selected from O, S and N and having a total of from 3 to 30 carbon atoms and/or heteroatoms; a substituted or unsubstituted aryl radical, having a total of from 6 to 30 carbon atoms; a substituted or unsubstituted heteroaryl radical, having a total of from 5 to 30 carbon atoms and/or heteroatoms, selected from O, S and N; or a group with donor or acceptor action;
or
R1 and R2, R3 and R4 and/or R6 and R7 may form, independently of each other, together with the carbon atoms to which they are bonded, a saturated or unsaturated or aromatic, optionally substituted ring, which is optionally interrupted by at least one heteroatom, selected from O, S and N, has a total of from 5 to 18 carbon atoms and/or heteroatoms, and may optionally be fused to at least one further optionally substituted saturated or unsaturated or aromatic ring, optionally interrupted by at least one heteroatom, selected from O, S and N, and having a total of from 5 to 18 carbon atoms and/or heteroatoms;
R5
is a linear or branched, substituted or unsubstituted alkyl radical having from 1 to 20 carbon atoms, optionally interrupted by at least one heteroatom, selected from O, S and N; a substituted or unsubstituted cycloalkyl radical having a total of from 3 to 30 carbon atoms; a substituted or unsubstituted heterocyclo alkyl radical, interrupted by at least one heteroatom selected from O, S and N and having a total of from 3 to 30 carbon atoms and/or heteroatoms; a substituted or unsubstituted aryl radical, having a total of from 6 to 30 carbon atoms; a substituted or unsubstituted heteroaryl radical, having a total of from 5 to 30 carbon atoms and/or heteroatoms, selected from O, S and N; or a group with donor or acceptor action;
X is CH, CD or N;
Y is CR8 or N;
R8
is hydrogen; deuterium; a linear or branched, substituted or unsubstituted alkyl radical having from 1 to 20 carbon atoms, optionally interrupted by at least one heteroatom, selected from O, S and N; a substituted or unsubstituted cycloalkyl radical having a total of from 3 to 30 carbon atoms; a substituted or unsubstituted heterocyclo alkyl radical, interrupted by at least one heteroatom selected from O, S and N and having a total of from 3 to 30 carbon atoms and/or heteroatoms; a substituted or unsubstituted aryl radical, having a total of from 6 to 30 carbon atoms; a substituted or unsubstituted heteroaryl radical, having a total of from 5 to 30 carbon atoms and/or heteroatoms, selected from O, S and N; or a group with donor or acceptor action.

### Claim 2 (depends on 1)

The cyclometallated Ir complex according to claim 1, wherein
R1, R2, R3, R4, R6 and R7
are each independently hydrogen; deuterium; methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, sec-butyl, iso-butyl, cyclopentyl, cyclohexyl, OCH3, OCF3; phenyl, pyridyl, pyrimidyl, pyrazinyl, carbazolyl, dibenzofuranyl, dibenzothiophenyl, benzofuranyl and benzothiophenyl wherein the aforementioned radicals may be unsubstituted or substituted by methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, sec-butyl, iso-butyl, methoxy, CF3 or phenyl; or a group with donor or acceptor action, selected from F, CF3, CN and SiPh3; and
R5
is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, sec-butyl, iso-butyl, cyclopentyl, cyclohexyl, OCH3, OCF3; phenyl, pyridyl, pyrimidyl, pyrazinyl, wherein the aforementioned radicals may be substituted by methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, sec-butyl, iso-butyl, methoxy or phenyl or unsubstituted; or a group with donor or acceptor action, selected from CF3 and CN.

### Claim 3 (depends on 1)

The cyclometallated Ir complex according to claim 1, wherein
R1, R2, R3, R4, R6 and R7
are each independently hydrogen; deuterium; methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, sec-butyl, iso-butyl; phenyl, pyridyl, pyrimidyl, pyrazinyl, carbazolyl, dibenzofuranyl, dibenzothiophenyl, wherein the aforementioned radicals may be unsubstituted or substituted by methyl, ethyl, iso-propyl, tert-butyl, iso-butyl or methoxy; CF3 or CN; and
R5
is methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl; phenyl, tolyl or pyridyl.

### Claim 4 (depends on 1)

The cyclometallated Ir complex according to claim 1, wherein
X, Y are each independently CH, CD or N.

### Claim 5 (depends on 1)

The cyclometallated Ir complex according to claim 1, wherein
X is N; and
Y is CR8.

### Claim 6 (depends on 1)

The cyclometallated Ir complex according to claim 1, wherein
X is N; and
Y is N.

### Claim 7 (depends on 1)

The cyclometallated Ir complex according to claim 1, wherein
X is CH or CD; and
Y is CR8.

### Claim 8 (depends on 1)

The cyclometallated Ir complex according to claim 1, having one of the following formulae

### Claim 9 (depends on 1)

An organic electronic device comprising at least one cyclometallated Ir complex according to claim 1.

### Claim 10 (depends on 9)

The organic electronic device according to claim 9, wherein the organic electronic device is selected from an organic light-emitting diode (OLED), a light-emitting electrochemical cell (LEEC), an organic photovoltaic cell (OPV) and an organic field-effect transistor (OFET).

### Claim 11 (depends on 9)

The organic electronic device according to claim 9, wherein the cyclometallated Ir complex of formula (I) is employed in OLEDs or LEECs or in OPVs.

### Claim 12 (depends on 11)

The organic electronic device according to claim 11, wherein the OLED comprises
(a) an anode,
(b) a cathode,
(c) a light-emitting layer between the anode and the cathode,
(d) optionally a hole transport layer between the light-emitting layer and the anode,
wherein the cyclometallated Ir complex of formula (I) is present in the light-emitting layer and/or—if present—in the hole transport layer of the OLED.

### Claim 13 (depends on 9)

The organic electronic device according to claim 9, wherein the cyclometallated Ir complex of formula (I) is employed in combination with at least one host material.

### Claim 14 (depends on 1)

A light-emitting layer comprising at least one cyclometallated Ir complex of formula (I) as defined in claim 1 as emitter material.

### Claim 15 (depends on 1)

An organic light-emitting diode (OLED) comprising a cyclometallated Ir complex of formula (I) as defined in claim 1.

### Claim 16 (depends on 9)

An apparatus comprising the organic electronic device according to claim 9, wherein the apparatus is selected from the group consisting of a stationary visual display unit; a mobile visual display unit; an illumination unit; a unit in items of clothing; a unit in handbags, a unit in accessories, a unit in furniture and a unit in wallpaper.

### Claim 17 (depends on 1)

A process for preparing a cyclometallated Ir complex of formula (I) as defined in claim 1, by contacting suitable compounds comprising Ir with appropriate ligands or ligand precursors.

### Claim 18

An organic electronic device comprising at least one cyclometallated Ir complex selected from the group consisting of: