# US 10,374,162 B2 · Fullerene derivatives

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- Number: US 10,374,162 B2
- Document ID: US10374162B2
- Status: Granted
- Kind: B2
- Application number: 15/312,448
- Filed: 2015-05-26
- Published: 2017-03-30
- Granted: 2019-08-06
- Earliest claimed: 2014-06-17
- Assignees: Merck Patent GmbH; Nano-C, Inc.
- Applicants: Merck Patent GmbH; Nano-C, Inc.
- Inventors: Nicolas Blouin; Stephane Berny; Edward A. Jackson; Henning Richter
- Web page: https://patentgrep.com/patent/US10374162B2

## CPC

- C07C 35/44: with a hydroxy group on a condensed ring system having more than three rings
- C07C 69/12: Acetic acid esters
- C07C 69/157: containing six-membered aromatic rings
- C07C 69/16: of dihydroxylic compounds
- H10K 85/113: {Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene}
- H10K 85/151: {Copolymers}
- H10K 85/215: {comprising substituents, e.g. PCBM}
- H10N 10/856: comprising organic compositions
- C07C 2604/00: Fullerenes, e.g. C60 buckminsterfullerene or C70
- H10K 30/30: comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
- H10K 30/50: Photovoltaic [PV] devices
- Y02E 10/549: Organic PV cells
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- H10K: ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10N: ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

The invention relates to fullerene derivatives of formula I, to mixtures and formulations containing them, to the use of the fullerene derivatives, mixtures and formulations as organic semiconductors in, or for the preparation of electronic devices, especially organic photovoltaic (OPV) devices and organic photodetectors (OPD), and to electronic devices comprising, or being prepared from, these fullerene derivatives, mixtures or formulations.

## Claims

### Claim 1

A compound of formula I
wherein
Cn denotes a fullerene composed of n carbon atoms, optionally with one or more atoms trapped inside,
Adduct is a secondary adduct, or a combination of secondary adducts, appended to the fullerene Cn with any connectivity,
m is 0, an integer>1, or a non-integer>0,
o is an integer≥1,
ArS1 denotes an aryl or heteroaryl group with 5 to 20, preferably 5 to 15, ring atoms, which is mono- or polycyclic,
R1 to R6 denote, independently of each other, H, halogen, CN, R7, R8 or R9,
R7 denotes, on each occurrence identically or differently, a saturated or unsaturated, non-aromatic carbo- or heterocyclic group, or an aryl, heteroaryl, aryloxy or heteroaryloxy group, wherein each of the aforementioned groups has 3 to 20 ring atoms, is mono- or polycyclic, does optionally contain fused rings, and is optionally substituted by one or more halogen atoms or CN groups, or by one or more identical or different groups R8 or R9,
R8 denotes, on each occurrence identically or differently, an alkyl group with 1 to 30 C atoms, which is straight-chain, branched or cyclic, and in which one or more CH2 groups are optionally replaced by —O—, —S—, —C(═O)—, —C(═S)—, —C(═O)—O—, —O—C(═O)—, —NR0—, —C(═O)NR0—, —NR0—C(═O)—, —SiR0R00—, —CF2—, —CHR0═CR00—, —CY1═CY2— or —C≡C— in such a manner that O and/or S atoms are not linked directly to one another, and in which one or more H atoms are optionally replaced by F, Cl, Br, I or CN,
R9 denotes, on each occurrence identically or differently, a straight-chain, branched or cyclic alkyl group with 1 to 50, preferably 2 to 50, more preferably 2 to 25, most preferably 2 to 12, C atoms, in which one or more CH2 or CH3 groups are replaced by a cationic or anionic group,
Y1 and Y2 denote, independently of each other, H, F, Cl or CN,
R0 and R00 denote, independently of each other, H or an optionally substituted carbyl or hydrocarbyl group having 1 to 40 C atoms,
with the provisos that
a) at least one of R1, R2, R3 and R4 is different from H, and
b) if n=70, then R1 is different from —C(═O)—O—CH3 if R2 is H, and R2 is different from —C(═O)—O—CH3 if R1 is H, and
wherein when R1 , R2, R3 and R4 are different from H, they are selected from the following formulae
wherein
ArS2 denotes R7 or has one of the meanings of ArS1,
i is 0 or an integer from 1 to 9,
k is 0 or an integer from 1 to 9.

### Claim 2 (depends on 1)

The compound of claim 1, wherein n is 60 or 70.

### Claim 3 (depends on 1)

The compound of claim 1, wherein Cn, is a carbon based fullerene or an endohedral fullerene.

### Claim 4 (depends on 3)

The compound of claim 3, wherein Cn, is selected from (C60-Ih)[5,6]fullerene, (C70-D5h)[5,6]fullerene, (C76-D2*)[5,6]fullerene, (C84-D2*)[5,6]fullerene, (C84-D2d)[5,6]fullerene, La@C60, La@C82, Y@C82, Sc3N@C80, Y3N@C80, Sc3C2@C80 or a mixture of two or more of the aforementioned fullerenes.

### Claim 5 (depends on 1)

The compound according to claim 1, wherein m is 0 and o is 1.

### Claim 6 (depends on 1)

The compound according to claim 1, wherein the fullerene Cn is substituted at a [6,6] and/or [5,6] bond.

### Claim 7 (depends on 1)

The compound according to claim 1, wherein ArS1 is a benzene, thiophene or naphthalene group that is optionally substituted with one or more groups R5.

### Claim 8 (depends on 1)

The compound according to claim 1, wherein R2, R3 and R4 are H and R1 is selected from formulae P-RS-1 or P-RS-7 as defined in claim 1, wherein k is 0.

### Claim 9 (depends on 1)

The compound according to claim 1, wherein R3 and R4 are H.

### Claim 10 (depends on 1)

The compound according to claim 1, wherein one of R1 and R2 is H and the other is different from H.

### Claim 11 (depends on 1)

The compound according to claim 1, wherein R2, R3 and R4 are H and R1 is selected from formulae P-RS-1 to P-RS-7 as defined in claim 1, preferably from formula P-RS-1 or P-RS-7 wherein preferably k is 0.

### Claim 12 (depends on 11)

The compound according to claim 11, wherein n is 60.

### Claim 13 (depends on 1)

The compound according to claim 1, wherein R5 and R6 are H.

### Claim 14 (depends on 1)

A method comprising using a compound of claim 1 as electron acceptor or n-type semiconductor in a semiconducting material, organic electronic device or component of an organic electronic device.

### Claim 15 (depends on 1)

A composition comprising two or more fullerene derivatives, one or more of which is a compound of claim 1.

### Claim 16 (depends on 1)

A composition comprising one or more compounds of claim 1 as electron acceptor or n-type semiconductor component, and further comprising one or more semiconducting compounds which have electron donor or p-type properties.

### Claim 17 (depends on 1)

A composition comprising one or more compounds of claim 1 and one or more p-type organic semiconductor compounds selected from conjugated organic polymers.

### Claim 18 (depends on 1)

A composition comprising one or more compounds of claim 1 and one or more compounds which are selected from compounds having one or more of a semiconducting, charge transport, hole transport, electron transport, hole blocking, electron blocking, electrically conducting, photoconducting, photoactive and light emitting property.

### Claim 19 (depends on 1)

A method comprising using a compound of claim 1 as semiconducting, charge transport, electrically conducting, photoconducting, photoactive, thermoelectric material or light emitting material, or in an electronic device, or in a component of such an electronic device or in an assembly comprising such an electronic device or such a component.

### Claim 20 (depends on 1)

A semiconducting, charge transport, electrically conducting, photoconducting, photoactive, thermoelectric or light emitting material, which comprises a compound of claim 1.

### Claim 21 (depends on 1)

A formulation comprising a compound of claim 1, and further comprising one or more organic solvents.

### Claim 22 (depends on 21)

An electronic device, or a component thereof, or an assembly comprising it, which is prepared using a formulation of claim 21.

### Claim 23 (depends on 1)

An electronic device, or a component thereof, or an assembly comprising it, which comprises a compound of claim 1.

### Claim 24 (depends on 22)

The electronic device according to claim 22, which is an optical, electrooptical, electronic, electroluminescent, photoluminescent, photoactive or thermoelectric device.

### Claim 25 (depends on 22)

The electronic device according to claim 22, which is selected from organic field effect transistors (OFET), organic thin film transistors (OTFT), organic light emitting diodes (OLED), organic light emitting transistors (OLET), organic photovoltaic devices (OPV), organic photodetectors (OPD), organic solar cells, dye sensitized solar cells (DSSC), perovskite-based solar cells, thermoelectric devices, laser diodes, Schottky diodes, photoconductors and photodetectors.

### Claim 26 (depends on 23)

The component of claim 23, which is selected from charge injection layers, charge transport layers, interlayers, planarising layers, antistatic films, polymer electrolyte membranes (PEM), conducting substrates and conducting patterns.

### Claim 27 (depends on 23)

The assembly of claim 23, which is selected from integrated circuits (IC), radio frequency identification (RFID) tags or security markings or security devices containing them, flat panel displays or backlights thereof, electrophotographic devices, electrophotographic recording devices, organic memory devices, sensor devices, biosensors and biochips.

### Claim 28 (depends on 25)

The electronic device according to claim 25, which is a bulk heterojunction (BHJ) OPV device or an inverted BHJ OPV device.

### Claim 29 (depends on 17)

A bulk heterojunction which comprises, or is being formed from, the composition of claim 17.

### Claim 30 (depends on 1)

The compound according to claim 1, wherein R2, R3 and R4 are H and R1 is selected from formulae P-RS-1 or P-RS-7 as defined in claim 1.