# US 12,193,325 B2 · Nitrogen-containing heterocycles for use in OLEDs

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- Number: US 12,193,325 B2
- Document ID: US12193325B2
- Status: Granted
- Kind: B2
- Application number: 16/466,655
- Filed: 2017-12-04
- Published: 2020-02-27
- Granted: 2025-01-07
- Earliest claimed: 2016-12-05
- Assignees: Merck Patent GmbH
- Applicants: Merck Patent GmbH
- Inventors: Amir Parham; Jonas Kroeber; Dominik Joosten; Aurélie Ludemann; Tobias Grossmann; Philipp Stoessel; Christian Eickhoff
- Web page: https://patentgrep.com/patent/US12193325B2

## CPC

- H10K 85/657: {Polycyclic condensed heteroaromatic hydrocarbons}
- C07D 403/04: directly linked by a ring-member-to-ring-member bond
- C07D 403/14: containing three or more hetero rings
- C07D 471/06: Peri-condensed systems
- C07D 471/16: Peri-condensed systems
- C07D 491/06: Peri-condensed systems
- C07D 491/16: Peri-condensed systems
- C07D 493/04: Ortho-condensed systems
- C07D 493/12: in which the condensed system contains three hetero rings
- C07D 495/02: in which the condensed system contains two hetero rings
- C07D 495/06: Peri-condensed systems
- C07D 495/12: in which the condensed system contains three hetero rings
- C07D 495/16: Peri-condensed systems
- C07D 495/22: in which the condensed system contains four or more hetero rings
- C07D 519/00: Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
- C09K 11/06: containing organic luminescent materials
- 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 2211/1018: Heterocyclic compounds
- H10K 50/11: characterised by the electroluminescent [EL] layers
- H10K 2101/10: Triplet emission
- Y02E 10/549: Organic PV cells
- H10K: ORGANIC ELECTRIC SOLID-STATE DEVICES
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)
- C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

The present invention describes nitrogen-containing heterocycles substituted by carbazole groups, especially for use in electronic devices. The invention further relates to a process for preparing the compounds of the invention and to electronic devices comprising these.

## Claims

### Claim 1

Compound comprising at least one structure of the (IIIa), (IIIb), (IIIc) or (IIId)
where in Formula (IIIa), (IIIb), (IIIc), and (IIId) W1 is SO, SO2, Si(R1)2 or C═O;
where in Formulae (IIIa), (IIIb), (IIIc), and (IIId), the symbols used are as follows:
X is the same or different at each instance and is N or CR1;
X1 is N or CR1 where at least one X1 group is N;
R1 is the same or different at each instance and is H, D, F, Cl, Br, I, CN, NO2, OAr1OR2, SAr1, SR2, C(═O)Ar1, C(═O)R2, P(═O)(Ar1)2, P(Ar1)2, B(Ar1)2, Si(Ar1)3, Si(R2)3, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms or an alkenyl group having 2 to 40 carbon atoms, each of which may be substituted by one or more R2 radicals, and where one or more nonadjacent CH2 groups 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 where one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and may be substituted in each case by one or more R2 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R2 radicals, or an aralkyl or heteroaralkyl group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R2 radicals; at the same time, two or more R′ substituents together may also form a mono- or polycyclic, aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system with the proviso that a substituent R1 does not form a ring system with a substituent R2;
Ar1 is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 5 to 30 aromatic ring atoms and may be substituted by one or more nonaromatic R2 radicals; at the same time, it is possible for two Ar1 radicals bonded to the same silicon atom, nitrogen atom, phosphorus atom or boron atom also to be joined together via a bridge by a single bond or a bridge selected from B(R2), C(R2)2, Si(R2)2, C═O, C═NR2, C═C(R2)2, O, S, S═O, SO2, N(R2), P(R2) and P(═O)R2;
R2 is the same or different at each instance and is H, D, F, Cl, Br, I, CN, B(OR3)2, OR3, SR3, NO2, C(═O)R3, CR3═C(R3)2, C(═O)OR3, C(═O)N(R3)2, Si(R3)3, P(R3)2, B(R13)2, N(R3)2, NO2, P(═O)(R3)2, OSO2R3, OR3, S(═O) R3, S(═O)2R3, straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, each of which may be substituted by one or more R3 radicals, and where one or more nonadjacent CH2 groups may be replaced by -R3C═CR3-, —C≡C—, Si(R3)2, C═O, C═S, C═NR3, —C(═O)O—, —C(═O)NR3, NR3, P(═O) (R3), —O—, —S—, SO or SO2 and where one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and may be substituted in each case by one or more R3 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R3 radicals; at the same time, two or more R2 substituents together may also form a mono- or polycyclic, aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system with the proviso that a substituent R2 does not form a ring system with a substituent R1;
R3 is the same or different at each instance and is selected from the group consisting of H, D, F, CN, an aliphatic hydrocarbyl radical having 1 to 20 carbon atoms, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms in which one or more hydrogen atoms may be replaced by D, F, Cl, Br, I or CN and which may be substituted by one or more alkyl groups each having 1 to 4 carbon atoms; at the same time, it is possible for two or more R3 substituents together to form a mono- or polycyclic, aliphatic ring system;
where m is 4;
wherein, if two adjacent substituents R1 form an aromatic or heteroaromatic ring system, at least one such ring system is selected from the groups of formula (DB-1)
where X2 is the same or different at each instance and is N or CR2, Y1 is O, S, C(R2)2, or NR2 and the dotted lines represent direct bonds to the formula (IIIa), (IIIb), (IIIc), or (IIId);
wherein if Y1 in DB-1 is C(R2)2, the R2 in the C(R2)2, in DB-1 does not form a mono- or polycyclic, aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system.

### Claim 2 (depends on 1)

Compound according to claim 1, comprising at least one structure of the formula (IVa), (IVb), (IVc) or (IVd)
wherein m is 4, n is 3, and X1 is N or CR1 where at least one X1 group is N.

### Claim 3 (depends on 2)

Compound according to claim 2, comprising at least one structure of the formula (Va), (Vb), (Vc) or (Vd)
where m is 4, and n is 3.

### Claim 4 (depends on 1)

Compound according to claim 1, characterized in that two adjacent R1 radicals form a ring of the formula (DB-1) and optionally two adjacent R1 form a ring of formula (DB-2) or (DB-3)
where X2 is the same or different at each instance and is N or CR2, Y1 and Y2 independently at each instance are O, S, (CR2)2 or NR2 and the dotted lines represent bonds to the formula (IIIa), (IIIb), (IIIc), or (IIId), where X1 and R2 have the definition given in claim 1.

### Claim 5 (depends on 4)

Compound according to claim 4, comprising at least one structure of the formula (VIa), (VIb), (VIc) or (VId)
where the symbols X1 and X2 have the definition given in claim 4, l is 2, m is 4 and X1 is N or CR1, where at least one X1 group adjacent to the carbon atom to which the carbazole derivative group is bonded is N.

### Claim 6 (depends on 5)

Compound according to claim 5, comprising at least one structure of the formula (VIIa), (VIIb), (VIIc), (VIId), (XIIIa), (XIIIb), (XIIIc) or (XIIId)
where m is 4, and X1 is N or CR1, where at least one X1 group is N.

### Claim 7 (depends on 6)

Compound according to claim 6, comprising at least one structure of the formula (VIIIa), (VIIIb), (VIIIc), (VIIId), (XIVa), (XIVb), (XIVc) or (XIVd)
where l is 2, n is 3 and m is 4.

### Claim 8 (depends on 1)

Compound according to claim 1, characterized in that not more than four X groups are N.

### Claim 9 (depends on 1)

Composition comprising at least one compound according to claim 1 and at least one further compound selected from the group consisting of fluorescent emitters, phosphorescent emitters, emitters that exhibit TADF, host materials, electron transport materials, electron injection materials, hole conductor materials, hole injection materials, electron blocker materials and hole blocker materials.

### Claim 10 (depends on 1)

Formulation comprising at least one compound according to claim 1 and at least one solvent.

### Claim 11 (depends on 1)

Use of a compound according to claim 1, in an electronic device.

### Claim 12 (depends on 1)

Process for preparing a compound according to claim 1, characterized in that, in a coupling reaction, a compound comprising at least one nitrogen-containing heterocyclic group is joined a compound comprising at least one carbazole group.

### Claim 13 (depends on 1)

Electronic device comprising at least one compound according to claim 1, wherein the electronic device is selected from the group consisting of organic electroluminescent devices, organic integrated circuits, organic field-effect transistors, organic thin-film transistors, organic light-emitting transistors, organic solar cells, organic optical detectors, organic photoreceptors, organic field quench devices, light-emitting electrochemical cells and organic laser diodes.