# US 10,374,167 B2 · Compound with novel six-membered ring structure for use in organic electronic devices

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- Number: US 10,374,167 B2
- Document ID: US10374167B2
- Status: Granted
- Kind: B2
- Application number: 15/036,311
- Filed: 2014-10-20
- Published: 2016-10-13
- Granted: 2019-08-06
- Earliest claimed: 2013-11-15
- Assignees: Merck Patent GmbH
- Applicants: Merck Patent GmbH
- Inventors: Philipp Stoessel; Amir Hossain Parham; Christof Pflumm; Anja Jatsch
- Web page: https://patentgrep.com/patent/US10374167B2

## CPC

- C07D 209/86: with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
- C07D 219/14: with hydrocarbon radicals, substituted by nitrogen atoms, attached to the ring nitrogen atom
- C07D 307/87: Benzo [c] furans; Hydrogenated benzo [c] furans
- C07D 471/04: Ortho-condensed systems
- C07D 487/04: Ortho-condensed systems
- C07D 491/107: with only one oxygen atom as ring hetero atom in the oxygen-containing ring
- C09K 11/06: containing organic luminescent materials
- H10K 50/12: comprising dopants
- H10K 85/60: Organic compounds having low molecular weight (H10K85/10 - H10K85/50 take precedence)
- 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 85/636: {comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom}
- H10K 85/657: {Polycyclic condensed heteroaromatic hydrocarbons}
- H10K 85/6572: {comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole}
- 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 2211/1033: with oxygen
- C09K 2211/1044: containing two nitrogen atoms as heteroatoms
- C09K 2211/1088: containing oxygen as the only heteroatom
- H10K 50/11: characterised by the electroluminescent [EL] layers
- H10K 50/165: comprising dopants
- H10K 50/171: {Electron injection layers}
- H10K 50/18: Carrier blocking layers
- 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}
- Y02E 10/549: Organic PV cells
- Y02P 70/50: Manufacturing or production processes characterised by the final manufactured product
- 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
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

The present invention relates to novel compounds according to formula (I) having a six-membered ring structure substituted with electron donor, electron acceptor and sterically demanding groups. Said compound is suited for use in organic electronic devices, particularly in organic electroluminescent devices (OLEDs). Formula (I) wherein Q1 and Q2 are independently of each other selected from the group consisting of N, CRA, CRD, and CRS; Z1 and Z2 are independently of each other selected from the group consisting of N, CRA and CRD; RA is a group with −M-effect; RD is a group with +M-effect; and RS is a sterically demanding group, with the provision that the compound of general formula (I) comprises at least one group CRA and at least one group CRD.

## Claims

### Claim 1

A compound
selected from the group consisting of
wherein
RA wherein at each occurrence RA is independently of each other selected from the group consisting of fluoroalkyl, F, BR12, B(OR1)2, CHO, C(═O)R1, C(═O)OR1, C(═O)N(R1)2, CR1═C(CN)2, N3, NO2, P(═O)(R1)2, S(═O)R1, S(═O)2R1, heteroaryl, heteroaryl substituted with one or more electron withdrawing groups and aryl substituted with one or more electron withdrawing groups, wherein the electron withdrawing groups are selected from the group consisting of fluoroalkyl, F, B(OR1)2, CHO, C(═O)R1, CN, C(═O)OR1, C(═O)N(R1)2, NO2, P(═O)(R1)2, S(═O)R1, and S(═O)2R1;
RD is independently of each other of general formula (N-a)
Ar1′)m—NR12 (N-a)
wherein
Ar1′ is a substituted or unsubstituted aromatic with 6 to 30 aromatic ring atoms, or a heteroaromatic ring system with 5 to 30 aromatic ring atoms;
m is 0 or 1;
and
two RS together form a five-membered ring,
wherein two groups RS together form a five-membered ring of the following formulae (II-A)
A1 and A3 are at each occurrence independently selected from the group consisting of C(R3)2, O, S, NR3 and C(═O);
A2 is at each occurrence independently selected from the group consisting of C(R1)2, O, S, NR3 and C(═O); and in case two groups A2 are adjacent to each other, A2-A2 may also be selected from the group consisting of ortho-linked arylene- or heteroarylene-group with 5 to 14 aromatic ring atoms, each of which may independently of the other be substituted with R2 as defined above;
R1 is at each occurrence independently selected from the group consisting of H, D, F, Cl, Br, I, B(OR2)2, CHO, C(═O)R2, CR2═C(R2)2, CN, C(═O)OR2, C(═O)N(R2)2, Si(R2)3, N(R2)2, NO2, P(═O)(R2)2, OSO2R2, OR2, S(═O)R2, S(═O)2R2, OH, SH, linear alkyl-, alkoxy- or thioalkyl-group with 1 to 20 C-atoms or a branched or cyclic alkyl-, alkoxy- or thioalkyl-group with 3 to 20 C-atoms or a alkenyl- or alkinyl-group with 2 to 20 C-atoms, wherein the group may be substituted with one or more of groups R2 and wherein one or more CH2-groups in the group may be replaced by —R2C═CR2—, —C≡C—, Si(R2)2, C═O, C═S, C═NR2, C(═O)O—, C(═O)NR2—, NR2, P(═O)(R2), O, S, SO or SO2, and wherein one or more H-atoms in the group may be replaced by D, F, Cl, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, which can be substituted with one or more groups R2, or an aryloxy- or heteroaryloxy-group with 5 to 60 aromatic ring atoms, which can be substituted with one or more groups R2, or an aralkyl- or heteroaralkyl-group with 5 to 60 aromatic ring atoms, which can be substituted with one or more groups R2, wherein two or more groups R2 may be linked with each other and form an aliphatic or aromatic or heteroaromatic ring;
R2 is at each occurrence independently selected from the group consisting of H, D, F, alkyl having from 1 to 20 C-atoms, aromatic groups having from 1 to 20 aromatic carbon atoms and heteroaromatic groups having from 1 to 20 aromatic ring atoms, wherein the aromatic groups and the heteroaromatic groups may be substituted with an alkyl having from 1 to 20 carbon atoms; and
R3 is at each occurrence independently selected from the group consisting of F, linear alkyl- or alkoxy-group with 1 to 20 C-atoms, a branched or cyclic alkyl- or alkoxy-group with 3 to 20 C-atoms, each of which may be substituted with one or more of groups R2, wherein one or more non-adjacent CH2-groups may be replaced by R2C═CR2, C≡C, Si(R2)2, C═O, NR2, O, S or CONR2, and wherein one or more H-atom may be replaced with D or F, or an aromatic or heteroaromatic ring system with 5 to 24 aromatic ring atoms, each of which may each be substituted with one or more of groups R2, or an aryloxy- or heteroaryloxy-group with 5 to 24 aromatic ring atoms, which can be substituted with one or more groups R2, or an aralkyl- or heteroaralkyl-group with 5 to 24 aromatic ring atoms, which can be substituted with one or more groups R2, wherein two R2 bound to the same carbon atom may form an aliphatic or aromatic ring system and thus a spiro system; or R3 can form together with a neighboring group R1 or R2 an aliphatic ring system,
provided that in A1-A2-A3 no two heteroatoms are adjacent.

### Claim 2 (depends on 1)

The compound according to claim 1 of the formula (I-e).

### Claim 3 (depends on 1)

The compound according to claim 1, wherein at each occurrence RD is
Ar1)m—NAr22 (N-b)
wherein
Ar1 is a substituted or unsubstituted aromatic with 6 to 30 aromatic ring atoms, or a heteroaromatic ring system with 5 to 30 aromatic ring atoms;
Ar2 is a substituted or unsubstituted aromatic or heteroaromatic ring system with 5 to 30 aromatic carbon atoms, wherein the two groups Ar2 may be linked by a group Y, so that together with the N-atom of the NAr22-group, irrespective of any N-atoms that might be present in Ar2, a ring is formed;
Y is selected from the group consisting of a single bond, BR1, C(R1)2, Si(R1)2, NR1, PR1, P(═O)R1, P(═S)R1, O, S, S═O and S(═O)2; and
R1 is at each occurrence independently selected from the group consisting of H, D, F, Cl, Br, I, B(OR2)2, CHO, C(═O)R2, CR2═C(R2)2, CN, C(═O)OR2, C(═O)N(R2)2, Si(R2)3, N(R2)2, NO2, P(═O)(R2)2, OSO2R2, OR2, S(═O)R2, S(═O)2R2, OH, SH, linear alkyl-, alkoxy- or thioalkyl-group with 1 to 20 C-atoms or a branched or cyclic alkyl-, alkoxy- or thioalkyl-group with 3 to 20 C-atoms or a alkenyl- or alkinyl-group with 2 to 20 C-atoms, wherein the group may be substituted with one or more of groups R2 and wherein one or more CH2-groups in the group may be replaced by —R2C═CR2—, —C≡C—, Si(R2)2, C═O, C═S, C═NR2, C(═O)O, C(═O)NR2, NR2, P(═O)(R2), O, S, SO or SO2, and wherein one or more H-atoms in the group may be replaced by D, F, Cl, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, which can be substituted with one or more groups R2, or an aryloxy- or heteroaryloxy-group with 5 to 60 aromatic ring atoms, which can be substituted with one or more groups R2, or an aralkyl- or heteroaralkyl-group with 5 to 60 aromatic ring atoms, which can be substituted with one or more groups R2, wherein two or more groups R2 may be linked with each other and form an aliphatic or aromatic or heteroaromatic ring;
R2 is at each occurrence independently selected from the group consisting of H, D, F, alkyl having from 1 to 20 C-atoms, aromatic groups having from 1 to 20 aromatic carbon atoms and heteroaromatic groups having from 1 to 20 aromatic ring atoms, wherein the aromatic groups and the heteroaromatic groups may be substituted with an alkyl having from 1 to 20 carbon atoms; and
m is 0 or 1.

### Claim 4 (depends on 1)

The compound according to claim 1, wherein at each occurrence RD is independently of each other selected from the group consisting of groups of formula (N-b)
Ar1)m—NAr22 (N-b)
wherein
Ar1 is a substituted or unsubstituted aromatic with 6 to 30 aromatic ring atoms, or a heteroaromatic ring system with 5 to 30 aromatic ring atoms; and
NAr22 is selected from the group consisting of aromatic amines, heteroaromatic amines, carbazoles, azacarbazoles, annealed carbazoles, annealed azacarbazoles, 5,10-dihydro-phenazaboranes, 9,10-dihydroacridines, 9,10-dihydro-10-sila-acridines, 9,10-dihyddro-phenazine, 10-hydro-phenoxazine, and 10-hydro-phentiazine, all of which may be substituted or unsubstituted; and
m is 0 or 1.

### Claim 5 (depends on 4)

The compound according to claim 4, wherein in formula (N-b) the group NAr22 is selected from the group consisting of aromatic amines, heteroaromatic amines, carbazoles, azacarbazoles, annealed carbazoles, annealed azacarbazoles, 5,10-dihydro-phenazaboranes, 9,10-dihydroacridines, 9,10-dihydro-10-sila-acridines, 9,10-dihydro-phenazine, and 10-hydro-phenoxazine, and 10-hydro-phentiazine, all of which may be substituted or unsubstituted.

### Claim 6 (depends on 1)

The compound according to claim 1, comprising at least two identical groups RD.

### Claim 7 (depends on 1)

The compound according to claim 1 comprising at least two identical RA.

### Claim 8 (depends on 1)

An oligomer, polymer or dendrimer comprising one or more of the compounds of claim 1, wherein at least one bond to the oligomer, polymer or dendrimer is on any one or more of groups RA, RD or RS.

### Claim 9 (depends on 8)

A formulation comprising a solvent and the oligomer, polymer or dendrimer of claim 8.

### Claim 10 (depends on 8)

A method of producing an electronic device, said method comprising the steps of
(a) an oligomer, polymer or dendrimer of claim 8; and
(b) depositing said oligomer, polymer or dendrimer on a supporting layer.

### Claim 11 (depends on 1)

A formulation comprising a solvent and the compound of claim 1.

### Claim 12 (depends on 1)

A method of producing an electronic device, said method comprising the steps of
(a) providing the compound of claim 1; and
(b) depositing said compound on a supporting layer.

### Claim 13 (depends on 1)

An electronic device 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 photovoltaic cells, organic optical detectors, organic photoreceptors, organic field-quench-devices (OFQDs), organic light-emitting electrochemical cells (OLECs), organic laser diodes (O-Laser) and organic electroluminescence devices (OLEDs), characterized in that the electronic devices comprises the compound of claim 1.

### Claim 14 (depends on 1)

An organic electroluminescent device, comprising an anode, a cathode and at least one organic layer, said organic layer comprising the compound of claim 1 as matrix material in an emitting layer in combination with one or more dopants, or that it is comprised as electron transport material in an electron transport layer, an electron injection layer or a hole blocking layer.

### Claim 15 (depends on 1)

An organic electroluminescent device comprising an anode, a cathode and at least one organic layer, said organic layer comprising the compound of claim 1 as light emitting material.