# US 10,319,917 B2 · Phenoxasiline based compounds for electronic application

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- Number: US 10,319,917 B2
- Document ID: US10319917B2
- Status: Granted
- Kind: B2
- Application number: 14/440,637
- Filed: 2013-11-06
- Published: 2015-11-05
- Granted: 2019-06-11
- Earliest claimed: 2012-11-06
- Assignees: UDC Ireland Limited
- Applicants: UDC Ireland Limited
- Inventors: Soichi Watanabe; Christian Lennartz; Gerhard Wagenblast; Nicolle Langer; Junji Kido; Hisahiro Sasabe; Masato Kimura
- Web page: https://patentgrep.com/patent/US10319917B2

## CPC

- H10K 85/656: {comprising two or more different heteroatoms per ring (H10K85/652 takes precedence)}
- C07F 7/0816: {said ring comprising Si as a ring atom}
- C07F 9/6596: having atoms other than oxygen, sulfur, selenium, tellurium, nitrogen or phosphorus as ring hetero atoms
- H10K 85/342: {comprising iridium}
- H10K 85/40: Organosilicon compounds, e.g. TIPS pentacene
- H10K 85/626: {containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene}
- H10K 85/6574: {comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes}
- H10K 50/11: characterised by the electroluminescent [EL] layers
- H10K 50/12: comprising dopants
- H10K 50/15: Hole transporting layers
- H10K 50/16: Electron transporting layers
- H10K 50/171: {Electron injection layers}
- H10K 85/657: {Polycyclic condensed heteroaromatic hydrocarbons}
- H10K 85/6572: {comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole}
- H10K 2101/90: {Multiple hosts in the emissive layer}
- Y02E 10/549: Organic PV cells
- Y02P 20/582: Recycling of unreacted starting or intermediate materials
- 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)
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

Organic electronics applications, especially an organic light-emitting diode (OLED), an organic solar cell (organic photovoltaics) or a switching element such as an organic transistor, for example an organic FET (Field Effect Transistor) and an organic TFT (Thin Film Transistor), comprising at least one substituted phenoxasiline derivative, a organic semiconductor layer, a host material, electron/hole/exciton blocking material or electron/hole injection material comprising at least one substituted phenoxasiline derivative, the use of a substituted phenoxasiline derivative in organic electronics applications, an organic light-emitting diode, wherein at least one substituted phenoxasiline derivative is present in the electron/hole/exciton blocking layer, the electron/hole injection layer and/or the light-emitting layer, a light-emitting layer, an electron/hole/exciton blocking layer and an electron/hole injection layer comprising at least one substituted phenoxasiline derivative and a device selected from the group consisting of stationary visual display units, mobile visual display units; illumination units; keyboards; garments; furniture and wallpaper comprising at least one organic light-emitting diode, at least one light-emitting layer, at least one electron/hole/exciton blocking layer and/or at least one electron/hole injection layer according to the present invention.

## Claims

### Claim 1

An organic electronic device comprising at least one compound of the formula (I):
in which
R1, R2, R3, R4, R5, R6 and R7
are each independently hydrogen, C1-C20-alkyl, C3-C20-cycloalkyl, heterocycloalkyl having 3 to 20 ring atoms, C6-C30-aryl, heteroaryl having 5 to 30 ring atoms or a substituent with donor or acceptor action selected from the group consisting of C1-C20-alkoxy, C6-C30-aryloxy, C1-C20-alkylthio, C6-C30-arylthio, SiR10R11R12, halogen radicals, halogenated C1-C20-alkyl radicals, carbonyl (—CO(R1′)), carbonylthio (—C═O(SR10)), carbonyloxy (—C═O(OR10)), oxycarbonyl (—OC═O(R10)), thiocarbonyl (—SC═O(R10)), amino (—NR10R11), OH, pseudohalogen radicals, amido (—C═O(NR10R11)), —NR10C═O(R11), phosphonate (—P(O)(OR10)2), phosphate (—OP(O)(OR10)2), phosphine (—PR10R11), phosphine oxide (—P(O)R102), sulfate (—OS(O)2OR10), sulfoxide (—S(O)R10), sulfonate (—S(O)2OR10), sulfonyl (—S(O)2R10), sulfonamide (—S(O)2NR10R11), NO2, boronic esters (—OB(OR10)2), imino (—C═NR10), borane radicals, stannane radicals, hydrazine radicals, hydrazone radicals, oxime radicals, nitroso groups, diazo groups, vinyl groups, sulfoximines, alanes, germanes, boroxines and borazines;
or two adjacent R1, R2, R3, R4, R5, R6 or R7 radicals, in each case together with the carbon atoms to which they are bonded, form a ring having a total of 3 to 12 atoms, where the ring may be saturated or mono- or polyunsaturated and, as well as carbon atoms, may have one or more heteroatoms selected from N, O and P, where the ring may be unsubstituted or mono- or polysubstituted and/or may be fused to further 3- to 12-membered rings;
R8 and R9
are each independently C1-C20-alkyl, C3-C20-cycloalkyl, heterocycloalkyl having 3 to 20 ring atoms, C6-C30-aryl or heteroaryl having 5 to 30 ring atoms;
R10, R11, R12
are each independently C1-C20-alkyl, C3-C20-cycloalkyl, heterocycloalkyl having 3 to 20 ring atoms, C6-C30-aryl, heteroaryl having 5 to 30 ring atoms, —O—Si(C1-C20-alkyl)3, —O—Si(C6-C30-aryl)3, C1-C20-alkoxy or C6-C30-aryloxy;
or two adjacent R10 and R11, R10 and R12 or R11 and R12 radicals, together with the atom to which they are bonded, form a ring having a total of 3 to 12 atoms, where the ring may be saturated or mono- or polyunsaturated and, as well as the atom to which the R10, R11 or R12 radicals are bonded, may have exclusively carbon atoms or one or more further heteroatoms selected from N, O and P, where the ring may be unsubstituted or mono- or polysubstituted and/or may be fused to further 3- to 12-membered rings;
Y is C3-C20-cycloalkyl, heterocycloalkyl having 3 to 20 ring atoms, C6-C30-aryl, heteroaryl having 5 to 30 ring atoms or a substituent with donor or acceptor action selected from the group consisting of C1-C20-alkoxy, C6-C30-aryloxy, C1-C20-alkylthio, C6-C30-arylthio, SiR10R11R12, halogen radicals, halogenated C1-C20-alkyl radicals, carbonyl (—CO(R10)), carbonylthio (—C═O(SR10)), carbonyloxy (—C═O(OR10)), oxycarbonyl (—OC═O(R10)), thiocarbonyl (—SC═O(R10)), amino (—NR10R11), OH, pseudohalogen radicals, amido (—C═O(NR10R11)), —NR10C═O(R11), phosphonate (—P(O)(OR10)2), phosphate (—OP(O)(OR10)2), phosphine (—PR10R11), phosphine oxide (—P(O)R112), sulfate (—OS(O2)OR10), sulfoxide (—S(O)R10), sulfonate (—S(O)2OR10), sulfonyl (—S(O)2R10), sulfonamide (—S(O)2NR10R11), NO2, boronic esters (—OB(OR10)2), imino (—C═NR10), borane radicals, stannane radicals, hydrazine radicals, hydrazone radicals, oxime radicals, nitroso groups, diazo groups, vinyl groups, sulfoximines, alanes, germanes, boroxines and borazines.

### Claim 2 (depends on 1)

The organic electronic device according to claim 1, wherein
Y is heteroaryl having 5 to 30 ring atoms selected from the group consisting of pyrrolyl, furanyl, thienyl, and benzoanellated ring systems thereof and
R10, R11 and R12
are each independently C6-C30-aryl.

### Claim 3 (depends on 1)

The organic electronic device according to claim 1, wherein
Y is selected from the group consisting of
and SiPh3,
wherein
X is NR10, O or S,
R10 is C1-C20-alkyl, C3-C20-cycloalkyl, heterocycloalkyl having 3 to 20 ring atoms, C6-C30-aryl, heteroaryl having 5 to 30 ring atoms, —O—Si(C1-C20-alkyl)3, —O—Si(C6-C30-aryl)3, C1-C20-alkoxy or C6-C30-aryloxy; and
R13 is H or phenoxasilinyl of formula (I′),
wherein the substituents Y′, R2′, R3′, R4′, R5′, R7′, R8′ and R9′ have independently the same meanings as the substituents Y, R2, R3, R4, R5, R7, R8 and R9 in the phenoxasiline derivatives of formula (I),
and the symbol ˜ means that there is a binding site at the position marked with ˜.

### Claim 4 (depends on 1)

The organic electronic device according to claim 1, wherein
R8 and R9
are each independently C6-C30-aryl or heteroaryl having 5 to 30 ring atoms.

### Claim 5 (depends on 1)

The organic electronic device according to claim 1, wherein
R8 and R9 are identical.

### Claim 6 (depends on 1)

The organic electronic device according to claim 1, wherein R1, R2, R3, R4, R5, and R7 are each hydrogen and R6 is hydrogen or heteroaryl having 5 to 30 ring atoms selected from the group consisting of pyrrolyl, furanyl, thienyl, and benzoanellated ring systems thereof or SiR10R11R12; or
R1, R2; R5, and R7 are each hydrogen and R3 and R4 are each independently C1-C20-alkyl, C3-C20-cycloalkyl, heterocycloalkyl having 3 to 20 ring atoms, C6-C30-aryl, heteroaryl having 5 to 30 ring atoms, methoxy, phenyloxy, halogenated C1-C4-alkyl, halogen, CN, SiR10R11R12, P(O)Ph2 or diphenylamino and R6 is hydrogen or heteroaryl having 5 to 30 ring atoms selected from the group consisting of pyrrolyl, furanyl, thienyl, and benzoanellated ring systems thereof or SiR10R11R12.

### Claim 7 (depends on 6)

The organic electronic device according to claim 6, wherein the compound of formula (I) is selected from the compounds of formulae (Ia), (Ib), (Ic) and (Id)
wherein
Y and R6
are each independently heteroaryl having 5 to 30 ring atoms selected from the group consisting of pyrrolyl, furanyl, thienyl, and benzoanellated ring systems thereof or SiR10R11R12;
R3 and R4
are each independently C1-C20-alkyl, C3-C20-cycloalkyl, heterocycloalkyl having 3 to 20 ring atoms, C6-C30-aryl, heteroaryl having 5 to 30 ring atoms, methoxy, phenyloxy, halogenated C1-C4-alkyl, or halogen;
R10, R11 and R12
are each independently C6-C30-aryl;
and
R8 and R9
are each independently C6-C30-aryl or heteroaryl having 5 to 30 ring atoms.

### Claim 8 (depends on 1)

The organic electronic device according to claim 1, wherein
R1, R2, R3, R4, R5, and R7 are hydrogen, and
R6 is heteroaryl having 5 to 30 ring atoms selected from the group consisting of pyrrolyl, furanyl, thienyl, and benzoanellated ring systems thereof or SiR10R11R12, and
R10, R11 and R12
are each independently C6-C30-aryl.

### Claim 9 (depends on 1)

The organic electronic device according to claim 1, which is an OLED.

### Claim 10 (depends on 9)

The OLED according to claim 9 comprising an anode An and a cathode Ka and a light-emitting layer E arranged between the anode An and the cathode Ka, and optionally at least one further layer selected from the group consisting of at least one blocking layer for holes/excitons, at least one blocking layer for electrons/excitons, at least one hole injection layer, at least one hole conductor layer, at least one electron injection layer and at least one electron conductor layer, wherein the at least one compound of the formula (I) is present in the light-emitting layer E and/or when present, in at least one of the further layers.

### Claim 11 (depends on 9)

A device selected from the group consisting of stationary visual
display units; mobile visual display units; illumination units; keyboards; garments;
furniture and wallpaper comprising at least one OLED as claimed in claim 9.

### Claim 12 (depends on 1)

The organic electronic device according to claim 1, wherein the compound of formula (I) is employed as host material, electron/exciton transport material, hole/exciton transport material, hole/exciton blocker material, electron/exciton blocker material, hole/exciton injection material and/or electron/exciton injection material.

### Claim 13

A light-emitting layer, electron/exciton transport layer, hole/exciton transport layer, hole/exciton blocking layer, electron/exciton blocking layer, hole/exciton injection layer and/or electron/exciton injection layer comprising at least one compound of formula (I)
in which
R1, R2, R3, R4, R5, R6 and R7
are each independently hydrogen, C1-C20-alkyl, C3-C20-cycloalkyl, heterocycloalkyl having 3 to 20 ring atoms, C6-C30-aryl, heteroaryl having 5 to 30 ring atoms or a substituent with donor or acceptor action selected from the group consisting of C1-C20-alkoxy, C6-C30-aryloxy, C1-C20-alkylthio, C6-C30-arylthio, Sir10R11R12, halogen radicals, halogenated C1-C20-alkyl radicals, carbonyl))(—CO(R10)), carbonylthio))(—C═O(SR10)), carbonyloxy))(—C═O(OR10)), oxycarbonyl))(—OC═O(R10)), thiocarbonyl))(—SC═O(R10)), amino (—NR10R11), OH, pseudohalogen radicals, amido (—C═O(NR10R11)), —NR10C═O(R11), phosphonate (—P(O)(OR10), phosphate)(—OP(O)(OR10)2), phosphine (—PR10R11), phosphine oxide (—P(O)(R10)2), sulfate)(—OS(O)2OR10), sulfoxide)(—S(O)R10), sulfonate)(—S(O)2OR10), sulfonyl) (—S(O)2R10), sulfonamide (—S(O)2NR10R11), NO2, boronic esters)(—OB(OR10)2), imino (—C═NR10), borane radicals, stannane radicals, hydrazine radicals, hydrazone radicals, oxime radicals, nitroso groups, diazo groups, vinyl groups, sulfoximines, alanes, germanes, boroxines and borazines;
or two adjacent R1, R2, R3, R4, R5, R6 or R7radicals, in each case together with the carbon atoms to which they are bonded, form a ring having a total of 3 to 12 atoms, where the ring may be saturated or mono- or polyunsaturated and, as well as carbon atoms, may have one or more heteroatoms selected from N, O and P, where the ring may be unsubstituted or mono- or polysubstituted and/or may be fused to further 3- to 12-membered rings;
R8 and R9
are each independently C1-C20-alkyl, C1-C20-cycloalkyl, heterocycloalkyl having 3 to 20 ring atoms, C6-C30-aryl or heteroaryl having 5 to 30 ring atoms;
R10, R11, R12
are each independently C1-C20-alkyl, C1-C20-cycloalkyl, heterocycloalkyl having 3 to 20 ring atoms, C6-C30-aryl, heteroaryl having 5 to 30 ring atoms, —O-Si(C1-C20-alkyl)3, —O—Si(C6-C30-aryl)3, C1-C20-alkoxy or C6-C30-aryloxy;
or two adjacent R10 and R11, R10 and R12 or R11 and R12 radicals, together with the atom to which they are bonded, form a ring having a total of 3 to 12 atoms, where the ring may be saturated or mono- or polyunsaturated and, as well as the atom to which the R10, R11 or R12 radicals are bonded, may have exclusively carbon atoms or one or more further heteroatoms selected from N, O and P, where the ring may be unsubstituted or mono- or polysubstituted and/or may be fused to further 3- to 12-membered rings;
Y is C3-C20-cycloalkyl, heterocycloalkyl having 3 to 20 ring atoms, C6-C30-aryl, heteroaryl having 5 to 30 ring atoms or a substituent with donor or acceptor action selected from the group consisting of C1-C20-alkoxy, C6-C30-araloxy, C1-C20-alkylthio, C6-C30-arylthio, SiR10R11R12halogen radicals, halogenated C1-C20-alkyl radicals, carbonyl))(—CO(R10)), carbonylthio))(—C═O(SR10)), carbonyloxy))(—C═O(OR10)), oxycarbonyl))(—OC═O(R10)), thiocarbonyl))(—SC═O(R10)), amino (—NR10R11), OH, pseudohalogen radicals, amido (—C═O(NR10R11)), —NR10C═O(R11), phosphonate)(—P(O)(OR10)2), phosphate (—OP(O)(OR10)2), phosphine (—PR10R11), phosphine oxide)(—P(O)(R10)2), sulfate (—OS(O2)OR10), sulfoxide)(—S(O)R10), sulfonate)(—S(O)2OR10), sulfonyl)(—S(O)2R10), sulfonamide (—S(O),NR10R11), NO2, boronic esters)(—OB(OR10)2), imino)(—C═NR10), borane radicals, stannane radicals, hydrazine radicals, hydrazone radicals, oxime radicals, nitroso groups, diazo groups, vinyl groups, sulfoximines, alanes, germanes, boroxines and borazines.