# US 10,374,168 B2 · Materials for electronic devices

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- Number: US 10,374,168 B2
- Document ID: US10374168B2
- Status: Granted
- Kind: B2
- Application number: 15/303,390
- Filed: 2015-03-19
- Published: 2017-05-04
- Granted: 2019-08-06
- Earliest claimed: 2014-04-14
- Assignees: Merck Patent GmbH
- Applicants: Merck Patent GmbH
- Inventors: Jochen Pfister; Frank Voges; Elvira Montenegro; Teresa Mujica-Fernaud
- Web page: https://patentgrep.com/patent/US10374168B2

## CPC

- C07D 471/10: Spiro-condensed systems
- C09K 11/025: {non-luminescent particle coatings or suspension media}
- C09K 11/06: containing organic luminescent materials
- H10K 85/615: {Polycyclic condensed aromatic hydrocarbons, e.g. anthracene}
- H10K 85/633: {comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom}
- 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}
- C09K 2211/1007: Non-condensed systems
- C09K 2211/1011: Condensed systems
- C09K 2211/1014: bridged by heteroatoms, e.g. N, P, Si or B
- C09K 2211/1029: containing one nitrogen atom as the heteroatom
- 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 50/11: characterised by the electroluminescent [EL] layers
- H10K 50/15: Hole transporting layers
- H10K 50/155: comprising dopants
- H10K 50/17: Carrier injection layers
- H10K 50/181: {Electron blocking layers}
- H10K 85/624: {containing six or more rings}
- H10K 2101/10: Triplet emission
- Y02E 10/549: Organic PV cells
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)
- 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

The present application relates to heterospirobifluorene compounds, to a process for the preparation thereof, and to electronic devices, in particular organic electroluminescent devices, comprising the heterospirobifluorene derivatives.

## Claims

### Claim 1

A compound of the formula (I)
where the following applies to the symbols and indices occurring:
A is C;
Y is N;
X is on each occurrence, identically or differently, CR1 or N;
Ar1, Ar2 are on each occurrence, identically or differently, selected from the formula (Ar-2) to (Ar-15) and (Ar-18) to (Ar-66)
Ar3, Ar4, Ar5, Ar6 on each occurrence, identically or differently, conform to formula (Ar-1),
which is optionally substituted by one or more radicals R2 on the free positions, and where the bond denoted by * represents the bonding position of the respective group;
R1, R2 are selected on each occurrence, identically or differently, from H, D, F, C(═O)R3, CF3, OCF3, CN, Si(R3)3, N(R3)2, P(═O)(R3)2, OR3, S(═O)R3, S(═O)2R3, straight-chain alkyl or alkoxy groups having 1 to 20 C atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 C atoms, alkenyl or alkynyl groups having 2 to 20 C atoms, aromatic ring systems having 6 to 40 aromatic ring atoms and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more radicals R1 or R2 is optionally linked to one another and may form a ring; where the said alkyl, alkoxy, alkenyl and alkynyl groups and the said aromatic ring systems and heteroaromatic ring systems may each be substituted by one or more radicals R3; and where one or more CH2 groups in the said alkyl, alkoxy, alkenyl and alkynyl groups is optionally replaced by —R3C═CR3—, —C≡C—, Si(R3)2, C═O, C═NR3, —C(═O)O—, —C(═O)NR3—, NR3, P(═O)(R3), —O—, —S—, SO or SO2;
R3 is selected on each occurrence, identically or differently, from H, D, F, C(═O)R4, CF3, OCF3, CN, Si(R4)3, N(R4)2, P(═O)(R4)2, OR4, S(═O)R4, S(═O)2R4, straight-chain alkyl or alkoxy groups having 1 to 20 C atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 C atoms, alkenyl or alkynyl groups having 2 to 20 C atoms, aromatic ring systems having 6 to 40 aromatic ring atoms and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more radicals R3 is optionally linked to one another and may form a ring; where the said alkyl, alkoxy, alkenyl and alkynyl groups and the said aromatic ring systems and heteroaromatic ring systems may each be substituted by one or more radicals R4; and where one or more CH2 groups in the said alkyl, alkoxy, alkenyl and alkynyl groups is optionally replaced by —R4C═CR4—, —C≡C—, Si(R4)2, C═O, C═NR4, —C(═O)O—, —C(═O)NR4—, NR4, P(═O)(R4), —O—, —S—, SO or SO2;
R4 is selected on each occurrence, identically or differently, from H, D, F, CN, alkyl groups having 1 to 20 C atoms, aromatic ring systems having 6 to 40 aromatic ring atoms and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more radicals R4 is optionally linked to one another and may form a ring; and where the said alkyl groups, aromatic ring systems and heteroaromatic ring systems is optionally substituted by F or CN;
a, b, c, d are on each occurrence, identically or differently, 0 or 1; and
wherein at least one of the indices a, b, c and d is equal to 1.

### Claim 2

An oligomer, polymer or dendrimer containing one or more compounds of the formula (I)
where the following applies to the symbols and indices occurring:
A is C or Si;
Y is on each occurrence, identically or differently, N or P;
X is on each occurrence, identically or differently, CR1 or N;
Ar1, Ar2 are on each occurrence, identically or differently, an aromatic ring system having 6 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R2, or a heteroaromatic ring system having 5 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R2;
Ar3, Ar4, Ar5, Ar6 are on each occurrence, identically or differently, an aromatic ring system having 6 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R2, or a heteroaromatic ring system having 5 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R2;
R1, R2 are selected on each occurrence, identically or differently, from H, D, F, C(═O)R3, CF3, OCF3, CN, Si(R3)3, N(R3)2, P(═O)(R3)2, OR3, S(═O)R3, S(═O)2R3, straight-chain alkyl or alkoxy groups having 1 to 20 C atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 C atoms, alkenyl or alkynyl groups having 2 to 20 C atoms, aromatic ring systems having 6 to 40 aromatic ring atoms and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more radicals R1 or R2 is optionally linked to one another and may form a ring; where the said alkyl, alkoxy, alkenyl and alkynyl groups and the said aromatic ring systems and heteroaromatic ring systems may each be substituted by one or more radicals R3; and where one or more CH2 groups in the said alkyl, alkoxy, alkenyl and alkynyl groups is optionally replaced by —R3C═CR3—, —C≡C—, Si(R3)2, C═O, C═NR3, —C(═O)O—, —C(═O)NR3—, NR3, P(═O)(R3), —O—, —S—, SO or SO2;
R3 is selected on each occurrence, identically or differently, from H, D, F, C(═O)R4, CF3, OCF3, CN, Si(R4)3, N(R4)2, P(═O)(R4)2, OR4, S(═O)R4, S(═O)2R4, straight-chain alkyl or alkoxy groups having 1 to 20 C atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 C atoms, alkenyl or alkynyl groups having 2 to 20 C atoms, aromatic ring systems having 6 to 40 aromatic ring atoms and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more radicals R3 is optionally linked to one another and may form a ring; where the said alkyl, alkoxy, alkenyl and alkynyl groups and the said aromatic ring systems and heteroaromatic ring systems may each be substituted by one or more radicals R4; and where one or more CI2 groups in the said alkyl, alkoxy, alkenyl and alkynyl groups is optionally replaced by —R4C═CR4—, —C≡C—, Si(R4)2, C═O, C═NR4, —C(═O)O—, —C(═O)NR4—, NR4, P(═O)(R4), —O—, —S—, SO or SO2,
R4 is selected on each occurrence, identically or differently, from H, D, F, CN, alkyl groups having 1 to 20 C atoms, aromatic ring systems having 6 to 40 aromatic ring atoms and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more radicals R4 is optionally linked to one another and may form a ring; and where the said alkyl groups, aromatic ring systems and heteroaromatic ring systems is optionally substituted by F or CN;
a, b, c, d are on each occurrence, identically or differently, 0 or 1;
where at least one of the two groups Ar1 and Ar2 is an aromatic ring system having 12 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R2, or a heteroaromatic ring system having 12 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R2; and
wherein at least one of the indices a, b, c and d is equal to 1,
where the bond(s) to the polymer, oligomer or dendrimer is optionally localised at any position in formula (I) that are substituted by R1 or R2.

### Claim 3

A compound of the formula (I)
where the following applies to the symbols and indices occurring:
A is C;
Y is N;
X is on each occurrence, identically or differently, CR1 or N;
Ar1, Ar2 are on each occurrence, identically or differently, selected from the formula (Ar-2) to (Ar-15) and (Ar-18) to (Ar-66)
Ar3, Ar4, Ar5, Ar6 are on each occurrence, identically or differently, an aromatic ring system having 6 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R2, or a heteroaromatic ring system having 5 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R2;
R1, R2 are selected on each occurrence, identically or differently, from H, D, F, C(═O)R3, CF3, OCF3, CN, Si(R3)3, N(R3)2, P(═O)(R3)2, OR3, S(═O)R3, S(═O)2R3, straight-chain alkyl or alkoxy groups having 1 to 20 C atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 C atoms, alkenyl or alkynyl groups having 2 to 20 C atoms, aromatic ring systems having 6 to 40 aromatic ring atoms and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more radicals R1 or R2 is optionally linked to one another and may form a ring; where the said alkyl, alkoxy, alkenyl and alkynyl groups and the said aromatic ring systems and heteroaromatic ring systems may each be substituted by one or more radicals R3; and where one or more CH2 groups in the said alkyl, alkoxy, alkenyl and alkynyl groups is optionally replaced by —R3C═CR3—, —C≡C—, Si(R3)2, C═O, C═NR3, —C(═O)O—, —C(═O)NR3—, NR3, P(═O)(R3), —O—, —S—, SO or SO2;
R3 is selected on each occurrence, identically or differently, from H, D, F, C(═O)R4, CF3, OCF3, CN, Si(R4)3, N(R4)2, P(═O)(R4)2, OR4, S(═O)R4, S(═O)2R4, straight-chain alkyl or alkoxy groups having 1 to 20 C atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 C atoms, alkenyl or alkynyl groups having 2 to 20 C atoms, aromatic ring systems having 6 to 40 aromatic ring atoms and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more radicals R3 is optionally linked to one another and may form a ring; where the said alkyl, alkoxy, alkenyl and alkynyl groups and the said aromatic ring systems and heteararomatic ring systems may each be substituted by one or more radicals R4; and where one or more CH2 groups in the said alkyl, alkoxy, alkenyl and alkynyl groups is optionally replaced by —R4C═CR4—, —C≡C—, Si(R4)2, C═O, C═NR4, —C(═O)O—, —C(═O)NR4—, NR4, P(═O)(R4), —O—, —S—, SO or SO2;
R4 is selected on each occurrence, identically or differently, from H, D, F, CN, alkyl groups having 1 to 20 C atoms, aromatic ring systems having 6 to 40 aromatic ring atoms and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more radicals R4 is optionally linked to one another and may form a ring; and where the said alkyl groups, aromatic ring systems and heteroaromatic ring systems is optionally substituted by F or CN;
a, b, c, d are on each occurrence, identically or differently, 0 or 1; and
wherein at least one of the indices a, b, c and d is equal to 1.

### Claim 4 (depends on 3)

The compound according to claim 3, wherein the compound contains no arylamino group as substituent.

### Claim 5 (depends on 3)

The compound according to claim 3, wherein precisely 1, 2 or 3 indices selected from the indices a, b, c and d in formula (I) are equal to 1.

### Claim 6 (depends on 3)

The compound according to claim 3, wherein X is equal to CR1.

### Claim 7 (depends on 3)

The compound according to claim 3, wherein the groups Ar3, Ar4, Ar5, Ar6 occurring in the compound of the formula (I) are selected identically.

### Claim 8 (depends on 3)

The compound according to claim 3, wherein
R1 is selected on each occurrence, identically or differently, from H, D, F, CN, Si(R3)3, straight-chain alkyl or alkoxy groups having 1 to 10 C atoms, branched or cyclic alkyl or alkoxy groups having 3 to 10 C atoms, aromatic ring systems having 6 to 24 aromatic ring atoms and heteroaromatic ring systems having 5 to 24 aromatic ring atoms; where the said alkyl and alkoxy groups, the said aromatic ring systems and the said heteroaromatic ring systems may each be substituted by one or more radicals R3; and where one or more CH2 groups in the said alkyl or alkoxy groups may be replaced by —C≡C—, —R3C═CR3—, Si(R3)2, C═O, C═NR, —NR3—, —O—, —S—, —C(═O)O— or —C(═O)NR3—;
R2 is selected on each occurrence, identically or differently, from H, D, F, CN, Si(R3)3, straight-chain alkyl or alkoxy groups having 1 to 10 C atoms, branched or cyclic alkyl or alkoxy groups having 3 to 10 C atoms, aromatic ring systems having 6 to 24 aromatic ring atoms and heteroaromatic ring systems having 5 to 24 aromatic ring atoms; where the said alkyl and alkoxy groups, the said aromatic ring systems and the said heteroaromatic ring systems may each be substituted by one or more radicals R3; and where one or more CH2 groups in the said alkyl or alkoxy groups may be replaced by —C≡C—, —R3C═CR3-, Si(R3)2, C═O, C═NR3, —NR3—, —O—, —S—, —C(═O)O— or —C(═O)NR3—;
R3 is selected on each occurrence, identically or differently, from H, D, F, CN, Si(R4)3, straight-chain alkyl or alkoxy groups having 1 to 10 C atoms, branched or cyclic alkyl or alkoxy groups having 3 to 10 C atoms, aromatic ring systems having 6 to 24 aromatic ring atoms and heteroaromatic ring systems having 5 to 24 aromatic ring atoms; where the said alkyl and alkoxy groups, the said aromatic ring systems and the said heteroaromatic ring systems may each be substituted by one or more radicals R4; and where one or more CH2 groups in the said alkyl or alkoxy groups may be replaced by —C≡C—, —R4C═CR4—, Si(R4)2, C═O, C═NR4, —NR4—, —O—, —S—, —C(═O)O— or —C(═O)NR4— and
R4 is selected on each occurrence, identically or differently, from H, D, F, CN, alkyl groups having 1 to 20 C atoms, aromatic ring systems having 6 to 40 aromatic ring atoms and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; and where the said alkyl groups, aromatic ring systems and heteroaromatic ring systems is optionally substituted by F or CN.

### Claim 9 (depends on 3)

The compound according to claim 3, wherein at least one of the groups Ar1, Ar2, Ar3, Ar4, Ar5 and Ar6 contains at least one heteroaryl group having 5 to 20 aromatic ring atoms.

### Claim 10 (depends on 3)

The compound according to claim 3, wherein the compound of the formula (I) conforms to one of the formulae (I-1) to (I-3)
where the symbols and indices occurring are defined in accordance with claim 3.

### Claim 11 (depends on 3)

A process for the preparation of the compound according to claim 3, wherein the process comprises the following steps:
1) reacting a halogen-substituted diphenylamine derivative with an acridinone derivative in the presence of an organometallic compound to form an intermediate;
2) ring-closure reacting the intermediate formed in 1) to give a spirobisacridine derivative;
3) introducing an aryl or heteroaryl group on a free nitrogen atom of the spirobisacridine derivative by means of Buchwald coupling.

### Claim 12 (depends on 3)

The compound according to claim 3, wherein Ar3 to Ar6 are identically or differently on each occurrence selected from formulae (Ar-1) to Ar-66) wherein (Ar-1), (Ar-16) and (Ar-17) are as follows:

### Claim 13 (depends on 3)

The compound according to claim 3, wherein Ar1 and Ar2 are of the formula (Ar-2).

### Claim 14 (depends on 13)

The compound according to claim 13, wherein Ar3 to Ar6 conform to formula (Ar-1),
which is substituted by radicals R2 at one or more of the free positions, and where the bond denoted by * represents the bonding position of the respective group.

### Claim 15 (depends on 13)

The compound according to claim 13 wherein Ar3 to Ar6 are identically or differently on each occurrence selected from formulae (Ar-1) to Ar-66) wherein (Ar-1), (Ar-16) (Ar-17) are as follows:

### Claim 16 (depends on 15)

The compound according to claim 15, wherein
R1 is selected on each occurrence, identically or differently, from H, D, F, CN, Si(R3)3, straight-chain alkyl or alkoxy groups having 1 to 10 C atoms, branched or cyclic alkyl or alkoxy groups having 3 to 10 C atoms, aromatic ring systems having 6 to 24 aromatic ring atoms and heteroaromatic ring systems having 5 to 24 aromatic ring atoms; where the said alkyl and alkoxy groups, the said aromatic ring systems and the said heteroaromatic ring systems may each be substituted by one or more radicals R3; and where one or more CH2 groups in the said alkyl or alkoxy groups may be replaced by —C≡C—, —R3C═CR3—, Si(R3)2, C═O, C═NR3, —NR3—, —O—, —S—, —C(═O)O— or —C(═O)NR3—;
R2 is selected on each occurrence, identically or differently, from H, D, F, CN, Si(R3)3, straight-chain alkyl or alkoxy groups having 1 to 10 C atoms, branched or cyclic alkyl or alkoxy groups having 3 to 10 C atoms, aromatic ring systems having 6 to 24 aromatic ring atoms and heteroaromatic ring systems having 5 to 24 aromatic ring atoms; where the said alkyl and alkoxy groups, the said aromatic ring systems and the said heteroaromatic ring systems may each be substituted by one or more radicals R3; and where one or more CH2 groups in the said alkyl or alkoxy groups may be replaced by —C≡C—, —R3C═CR3, Si(R3)2, C═O, C═NR3, —NR3—, —O—, —S—, —C(═O)O— or —C(═O)NR3—;
R3 is selected on each occurrence, identically or differently, from H, D, F, C, CN, Si(R4)3, straight-chain alkyl or alkoxy groups having 1 to 10 C atoms, branched or cyclic alkyl or alkoxy groups having 3 to 10 C atoms, aromatic ring systems having 6 to 24 aromatic ring atoms and heteroaromatic ring systems having 5 to 24 aromatic ring atoms; where the said alkyl and alkoxy groups, the said aromatic ring systems and the said heteroaromatic ring systems may each be substituted by one or more radicals R4; and where one or more CH2 groups in the said alkyl or alkoxy groups may be replaced by —C≡C—, —R4C═CR4—, Si(R4)2, C═O, C═NR4, —NR4—, —O—, —S—, —C(═O)O— or —C(═O)NR4— and
R4 is selected on each occurrence, identically or differently, from H, D, F, CN, alkyl groups having 1 to 20 C atoms, aromatic ring systems having 6 to 40 aromatic ring atoms and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; and where the said alkyl groups, aromatic ring systems and heteroaromatic ring systems is optionally substituted by F or CN.

### Claim 17 (depends on 3)

A formulation comprising at least one compound according to claim 3 and at least one solvent.

### Claim 18 (depends on 3)

An electronic device comprising at least one compound according to claim 3.

### Claim 19 (depends on 18)

The electronic device according to claim 18, wherein the device is selected from the group consisting of organic integrated circuits (OICs), organic field-effect transistors (OFETs), organic thin-film transistors (OTFTs), organic light-emitting transistors (OLETs), organic solar cells (OSCs), organic optical detectors, organic photoreceptors, organic field-quench devices (OFQDs), organic light-emitting electrochemical cells (OLECs), organic laser diodes (O-lasers) and organic electroluminescent devices (OLEDs).

### Claim 20 (depends on 2)

An electronic device comprising at least one oligomer, polymer or dendrimer according to claim 2.

### Claim 21 (depends on 3)

An organic electroluminescent device comprising at least one compound according to claim 3 is present in a layer selected from hole-transport layers and emitting layers.

### Claim 22 (depends on 21)

The organic electroluminescent device according to claim 21, wherein the at least one compound is present in an emitting layer together with one or more phosphorescent emitters.

### Claim 23 (depends on 21)

The organic electroluminescent device according to claim 21, wherein the at least one compound is present in a hole-transport layer together with one or more p-dopants.