# US 10,374,172 B2 · Azabenzimidazole carbene complexes as efficiency booster in OLEDs

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- Number: US 10,374,172 B2
- Document ID: US10374172B2
- Status: Granted
- Kind: B2
- Application number: 14/778,174
- Filed: 2014-03-19
- Published: 2016-10-06
- Granted: 2019-08-06
- Earliest claimed: 2013-03-20
- Assignees: UDC Ireland Limited
- Applicants: UDC Ireland Limited
- Inventors: Stefan Metz; Soichi Watanabe; Thomas Geßner; Korinna Dormann; Peter Murer; Christian Lennartz; Ute Heinemeyer; Glauco Battagliarin
- Web page: https://patentgrep.com/patent/US10374172B2

## CPC

- C09K 11/06: containing organic luminescent materials
- C07F 15/0033: {Iridium compounds}
- H05B 33/10: Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
- H10K 50/11: characterised by the electroluminescent [EL] layers
- H10K 50/13: comprising stacked EL layers within one EL unit
- H10K 85/342: {comprising iridium}
- C09K 2211/1029: containing one nitrogen atom as the heteroatom
- C09K 2211/1044: containing two nitrogen atoms as heteroatoms
- C09K 2211/1088: containing oxygen as the only heteroatom
- C09K 2211/1092: containing sulfur as the only heteroatom
- C09K 2211/185: of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
- H10K 50/15: Hole transporting layers
- H10K 50/181: {Electron blocking layers}
- H10K 85/40: Organosilicon compounds, e.g. TIPS pentacene
- H10K 2101/10: Triplet emission
- Y02E 10/549: Organic PV cells
- C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- H05B: ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H10K: ORGANIC ELECTRIC SOLID-STATE DEVICES
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

An organic electronic device comprising at least one hole-transport material and/or at least one electron/exciton blocker material, wherein said at least one hole-transport material and/or said at least one electron/exciton blocker material is an Ir metal-carbene complex comprising one, two or three specific bidentate azabenzimidazole ligands; a hole transport layer or an electron/exciton blocking layer, comprising at least one Ir metal-carbene complex, comprising one, two or three specific bidentate azabenzimidazole ligands; 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 furniture and units in wallpaper, comprising the organic electronic device of the present invention or the hole transport layer or the electron/exciton blocking layer of the present invention; and the use of an Ir metal-carbene complex comprising one, two or three specific bidentate azabenzimidazole ligands according to the present invention as hole-transport material and/or electron/exciton blocker material.

## Claims

### Claim 1

An organic electronic device selected from organic light-emitting diodes (OLED), light-emitting electrochemical cells (LEEC), organic photovoltaic cells (OPV) and organic field-effect transistors (OFET),
comprising at least one hole-transport material and/or at least one electron/exciton blocker material, wherein said at least one hole-transport material and/or said at least one electron/exciton blocker material comprises at least one Ir metal-carbene complex of formula (II′)
wherein
R1, R2 and R3
are each independently hydrogen, deuterium, a linear or branched alkyl radical, optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having a total of from 1 to 20 carbon atoms and/or heteroatoms, a substituted or unsubstituted cycloalkyl radical, optionally bearing at least one functional group and having from 3 to 20 carbon atoms, a substituted or unsubstituted heterocyclo alkyl radical, interrupted by at least one heteroatom, optionally bearing at least one functional group and having a total of from 3 to 20 carbon atoms and/or heteroatoms, a substituted or unsubstituted aryl radical, optionally bearing at least one functional group and having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl radical, interrupted by at least one heteroatom, optionally bearing at least one functional group and having a total of from 5 to 18 carbon atoms and/or heteroatoms, a group with donor or acceptor action;
or
R1 and R2, or R2 and R3, form, independently of each other, together with a carbon atom to which they are bonded an optionally substituted saturated or unsaturated or aromatic ring, optionally interrupted by at least one heteroatom and having 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 and having a total of from 5 to 18 carbon atoms and/or heteroatoms;
A1 is CR4 or N;
A2 is CR5 or N;
A3 is CR6 or N;
A4 is CR7 or N;
A1′ is CR4′ or N;
A2′ is CR5′ or N;
A3′ is CR6′ or N;
A4′ is CR7′ or N;
R4, R5, R6, R7, R4′, R5′, R6′, and R7′
are each independently hydrogen, deuterium, a linear or branched alkyl radical, optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having a total of from 1 to 20 carbon atoms and/or heteroatoms, a substituted or unsubstituted cycloalkyl radical, optionally bearing at least one functional group and having from 3 to 20 carbon atoms, a substituted or unsubstituted heterocyclo alkyl radical, interrupted by at least one heteroatom, optionally bearing at least one functional group and having a total of from 3 to 20 carbon atoms and/or heteroatoms, a substituted or unsubstituted aryl radical, optionally bearing at least one functional group and having from 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl radical, interrupted by at least one heteroatom, optionally bearing at least one functional group and having a total of from 5 to 18 carbon atoms and/or heteroatoms, a group with donor or acceptor action;
or
R4 and R5, R5 and R6, R6 and R7, R4′ and R5′, R5′ and R6′, or R6′ and R7′, 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, 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 and having a total of from 5 to 18 carbon atoms and/or heteroatoms;
n is 3;
L is not present; and
o is 0;
wherein the OLED comprises
(a) an anode,
(b) a cathode,
(c) a light-emitting layer between the anode and the cathode,
(d) at least one layer, selected from a hole-transport layer (d1) and an electron/exciton blocking layer (d2), disposed between the anode (a) and the light-emitting layer (c);
wherein the at least one hole-transport material is present in the hole-transport layer of the OLED and/or the at least one electron/exciton blocker material is present in the electron/exciton blocking layer of the OLED.

### Claim 2 (depends on 1)

The organic electronic device according to claim 1, wherein the at least one hole-transport material is present in a hole transport layer of the organic electronic device and the at least one electron/exciton blocker material is present in an electron/exciton-blocking layer of the organic electronic device.

### Claim 3 (depends on 1)

The organic electronic device according to claim 1, wherein the radicals, groups and symbols in the at least one Ir metal-carbene complex have the following meanings:
R1, R2 and R3
are each independently hydrogen, a linear or branched alkyl radical, having from 1 to 6 carbon atoms, a substituted or unsubstituted aryl radical, having from 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl radical, having a total of from 5 to 18 carbon atoms and/or heteroatoms, a group with donor or acceptor action, selected from the group consisting of halogen radicals, CF3, CN, SiPh3 and SiMe3;
or
R1 and R2, or R2 and R3, form, independently of each other, together with a carbon atom to which they are bonded an optionally substituted saturated or unsaturated or aromatic ring, optionally interrupted by at least one heteroatom and having 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 and having a total of from 5 to 18 carbon atoms and/or heteroatoms;
A1 is CR4;
A2 is CR5;
A3 is CR6;
A4 is CR7;
A1′ is CR4′
A2′ is CR5′
A3 is CR6′
A4′ is CR7′
R4, R5, R6, R7, R4′, R5′, R6′ and R7′
are each independently hydrogen, deuterium, a linear or branched alkyl radical, optionally bearing at least one functional group, optionally interrupted by at least one heteroatom and having a total of from 1 to 20 carbon and/or heteroatoms, a substituted or unsubstituted aryl radical, having from 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl radical, having a total of from 5 to 18 carbon atoms and/or heteroatoms, a group with donor or acceptor action, selected from halogen radicals; CF3, CN and SiMe3;
or
R4 and R5, R5 and R6, R6 and R7, R4′ and R5′, R5′ and R6′, or R6′ and R7′, form, independently of each other, with the carbon atoms to which they are bonded, a saturated, unsaturated or aromatic, optionally substituted ring, which is optionally interrupted by at least one heteroatom, has a total of from 5 to 18 carbon atoms and/or heteroatoms and may optionally be fused by at least one further optionally substituted saturated or unsaturated aromatic ring, optionally interrupted by at least one heteroatom and having a total of from 5 to 18 carbon atoms and/or heteroatoms.

### Claim 4 (depends on 1)

The organic electronic device according to claim 1, wherein the at least one Ir metal-carbene complex has the formula (II′a)

### Claim 5 (depends on 1)

The organic electronic device according to claim 1, wherein the at least one hole-transport material and/or at least one electron/exciton blocker material comprises at least one metal oxide.

### Claim 6 (depends on 1)

The organic electronic device according to claim 1, wherein the light-emitting layer comprises at least one emitter material, which has an emission maximum λmax of from 400 to 500 nm.

### Claim 7 (depends on 1)

The organic electronic device according to claim 1, wherein the light-emitting layer comprises at least one phosphorescent emitter material.

### Claim 8 (depends on 6)

The organic electronic device according to claim 6, wherein the at least one emitter material is a compound of formula (IV)
wherein
M is Ir,
n′″ is 1, 2 or 3,
A9 is CR9 or N,
A10 is CR10 or N,
A11 is CR11 or N,
A12 is CR12 or N,
where 2 of A9, A10, A11 and A12 are nitrogen atoms and at least one carbon atom is present between two nitrogen atoms in the ring;
R8 is a linear or branched alkyl radical, having from 1 to 6 carbon atoms, a substituted or unsubstituted cycloalkyl radical, having from 3 to 20 carbon atoms, a substituted or unsubstituted aryl radical, having from 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl radical, having a total of from 5 to 18 carbon atoms and/or heteroatoms,
R9, R10, R11 and R12
are each independently hydrogen, a linear or branched alkyl radical having 1 to 6 carbon atoms, a substituted or unsubstituted cycloalkyl radical, having from 3 to 20 carbon atoms, a substituted or unsubstituted aryl radical having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl radical having a total of 5 to 18 carbon atoms and/or heteroatoms,
or
R10 and R11 form, together with the carbon atoms to which they are bonded, an optionally substituted, unsaturated ring optionally interrupted by at least one heteroatom and having a total of 5 to 18 carbon atoms and/or heteroatoms,
A5 is CR13 or N,
A6 is CR14 or N,
A7 is CR15 or N,
A8 is CR16 or N,
R13, R14, R15 and R16
are each independently hydrogen, a linear or branched alkyl radical, optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having a total of from 1 to 20 carbon atoms and/or heteroatoms, a substituted or unsubstituted cycloalkyl radical, optionally bearing at least one functional group and having from 3 to 20 carbon atoms, a substituted or unsubstituted heterocyclo alkyl radical, interrupted by at least one heteroatom, optionally bearing at least one functional group and having a total of from 3 to 20 carbon atoms and/or heteroatoms, a substituted or unsubstituted aryl radical, optionally bearing at least one functional group and having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl radical, interrupted by at least one heteroatom, optionally bearing at least one functional group and having a total of from 5 to 18 carbon atoms and/or heteroatoms, a group with donor or acceptor action;
L′ is a monoanionic bidentate ligand,
o″ is 0, 1 or 2; and
n′″+o″ is 3.

### Claim 9 (depends on 1)

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 furniture and units in wallpaper, wherein the apparatus comprises the organic electronic device according to claim 1.

### Claim 10 (depends on 1)

The device of claim 1, wherein the at least one layer is a hole transport layer or an electron/exciton blocking layer; and
wherein
R1, R2 and R3
are each independently hydrogen, a linear or branched alkyl radical, having from 1 to 6 carbon atoms, a substituted or unsubstituted aryl radical, having from 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl radical, having a total of from 5 to 18 carbon atoms and/or heteroatoms, a group with donor or acceptor action, selected from the group consisting of halogen radicals, CF3, CN, SiPh3 and SiMe3;
or
R1 and R2, or R2 and R3, form, independently of each other, together with a carbon atom to which they are bonded an optionally substituted saturated or unsaturated or aromatic ring, optionally interrupted by at least one heteroatom and having 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 and having a total of from 5 to 18 carbon atoms and/or heteroatoms;
A1 is CR4;
A2 is CR5;
A3 is CR6;
A4 is CR7;
A1′ is CR4′;
A2′ is CR5′;
A3′ is CR6′;
A4′ is CR7′;
R4, R5, R6, R7, R4′, R5′, R6′ and R7′
are each independently hydrogen, deuterium, a linear or branched alkyl radical, optionally bearing at least one functional group, optionally interrupted by at least one heteroatom and having a total of from 1 to 20 carbon and/or heteroatoms, a substituted or unsubstituted aryl radical, having from 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl radical, having a total of from 5 to 18 carbon atoms and/or heteroatoms, a group with donor or acceptor action, selected from halogen radicals; CF3, CN and SiMe3;
or
R4 and R5, R5 and R6, R6 and R7, R4′ and R5′, R5′ and R6′, or R6′ and R7′, form, independently of each other, with the carbon atoms to which they are bonded, a saturated, unsaturated or aromatic, optionally substituted ring, which is optionally interrupted by at least one heteroatom, has a total of from 5 to 18 carbon atoms and/or heteroatoms and may optionally be fused by at least one further optionally substituted saturated or unsaturated aromatic ring, optionally interrupted by at least one heteroatom and having a total of from 5 to 18 carbon atoms and/or heteroatoms.

### Claim 11 (depends on 1)

The organic electronic device according to claim 1, further comprising Ir(DPBIC)3.