Cyclohexadiene fullerene derivatives

Patent metadata

Field	Value
Publication number	US-9543523-B2
Application number	US-201414483488-A
Country	US
Kind code	B2
Filing date	Sep 11, 2014
Priority date	Sep 11, 2013
Publication date	Jan 10, 2017
Grant date	Jan 10, 2017

Abstract

The invention relates to novel fullerene derivatives, to methods for their preparation and educts or intermediates used therein, 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, organic electronic (OE) devices, especially organic photovoltaic (OPV) devices and organic photodetectors (OPD), and to OE, OPV and OPD devices comprising, or being prepared from, these fullerene derivatives, mixtures or formulations.

First claim

The invention claimed is:

1. A compound of formula I

wherein
C n is 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 C n with any connectivity,
m is 0, an integer ≧1, or a non-integer >0,
o is an integer ≧1,
R 1 , R 2 , R 3 , R 4 independently of each other denote H, halogen, CN, R 5 or R 6 ,
R 5 denotes 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 R 6 ,
R 6 denotes an alkyl group with 1 to 30 C atoms, which is straight-chain, branched or cyclic, and in which one or more CH 2 groups are each optionally replaced by —O—, —S—, —C(═O)—, —C(═S)—, —C(═O)—O—, —O—C(═O)—, —NR 0 —, —C(═O)—NR 0 —, —NR 0 —C(═O)—, —SiR 0 R 00 —, —CF 2 —, —CHR 0 ═CR 00 —, —CY 1 ═CY 2 — 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 each optionally replaced by F, Cl, Br, I or CN,
Y 1 and Y 2 denote independently of each other H, F, Cl or CN, and
R 0 and R 00 denote independently of each other H or an optionally substituted carbyl or hydrocarbyl group with 1 to 40 C atoms,
wherein at least one of R 1 , R 2 , R 3 and R 4 denotes R 5 that is substituted by one or more groups R 6 as defined above, which have at least 3 C atoms wherein at least one CH 2 group is optionally replaced by —O—, —S—, —C(═O)—, —C(═S)—, —C(═O)—O—, —O—C(═O)—, —NR 0 —, —SiR 0 R 00 —, —CF 2 —, —CHR 0 ═CR 00 —, —CY 1 ═CY 2 — or —C≡C—.

2. The compound of claim 1 , wherein n is 60, 70, 76, 78, 82, 84, 90, 94 or 96.

3. The compound of claim 2 , wherein n is 60 or 70.

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

5. The compound of claim 4 , wherein C n is selected from (C 60-Ih )[5,6]fullerene, (C 70-D5h )[5,6]fullerene, (C 76-D2* )[5,6]fullerene, (C 84-D2* )[5,6]fullerene, (C 84-D2d )[5,6]fullerene, La@C 60 , La@C 82 , Y@C 82 , Sc 3 N@C 80 , Y 3 N@C 80 , Sc 3 C 2 @C 80 or a mixture of two or more of the aforementioned fullerenes.

6. The compound according to claim 1 , wherein R 1 , R 2 , R 3 and R 4 are independently of each other selected from H, halogen, CN, straight-chain, branched or cyclic alkyl with 1 to 30 C atoms, in which one or more CH 2 groups are each optionally replaced by —O—, —S—, —C(O)—, —C(S)—, —C(O)—O—, —O—C(O)—, —NR 0 —, —SiR 0 R 00 —, or —CF 2 —, or a carbocyclic or heterocyclic group selected from the following formulae

wherein
R 0 and R 00 are as defined in claim 1 ,
R 000 denotes an optionally substituted carbyl or hydrocarbyl group with 1 to 40 C atoms,
R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 independently of each other denote H, halogen, CN, or an alkyl group with 1 to 30 C atoms, which is straight-chain, branched or cyclic, and in which one or more CH 2 groups are each optionally replaced by —O—, —S—, —C(═O)—, —C(═S)—, —C(═O)—O—, —O—C(═O)—, —NR 0 —, —C(═O)—NR 0 —, —NR 0 —C(═O)—, —SiR 0 R 00 —, —CF 2 —, —CHR 0 ═CR 00 —, —CY 1 ═CY 2 — 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 each optionally replaced by F, Cl, Br, I or CN, and
wherein in each of the aforementioned formulae at least one of R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 is different from H.

7. The compound according to claim 1 , wherein R 1 , R 2 , R 3 and R 4 are independently of each other selected from H, straight-chain branched or cyclic alkyl with 1 to 30 C atoms, —O—, —COOR 000 , —COR 000 , CONR 0 R 000 , —F, —Cl, —NR 0 R 000 or a carbocyclic or heterocyclic group selected from the following formulae

wherein
R 0 and R 00 are as in claim 1 ,
R 000 denoted an optionally substituted carbyl or hydrocarbyl group with 1 to 40 C atoms,
R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 independently of each other denote H, halogen, CN, or an alkyl group with 1 to 30 C atoms, which is straight-chain, branched or cyclic, and in which one or more CH 2 groups are each optionally replaced by —O—, —S—, —C(═O)—, —C(═S)—, —C(═O)—O—, —O—C(═O)—, —NR 0 —, —C(═O)—NR 0 —, —NR 0 —C(═O)—, —SiR 0 R 00 —, —CF 2 —, —CHR 0 ═CR 00 —, —CY 1 ═CY 2 — 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 each optionally replaced by F, Cl, Br, I or CN, and
wherein in each of the aforementioned formulae at least one of R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 is different from H.

8. The compound according to claim 1 , wherein R 6 , on each occurrence identically or differently, is selected from straight-chain, branched or cyclic alkyl with 3 to 30 C atoms, in which one or more CH 2 groups are each optionally replaced by —O—, —S—, —C(O)—, —C(S)—, —C(O)—O—, —O—C(O)—, —NR 0 —, —SiR 0 R 00 or —CF 2 —, and wherein one or more H atoms are each optionally replaced by fluorine atoms, wherein R 0 and R 00 are as defined in claim 1 .

9. The compound of claim 1 , wherein R 0 and R 00 denote H or an alkyl group with 1 to 12 C atoms.

10. The compound of claim 6 , wherein R 000 denotes an alkyl group with 1 to 12 C atoms.

11. The compound of claim 1 , wherein the fullerene C n is substituted at a [6,6] and/or [5,6] bond.

12. The compound of claim 1 , wherein m is >0.

13. The compound of claim 12 , wherein the secondary adduct is selected from the following formulae

wherein
R S1 , R S2 , R S3 , R S4 and R S5 independently of each other denote H, halogen, CN, 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 R 6 , or an alkyl group with 1 to 30 C atoms, which is straight-chain, branched or cyclic, and in which one or more CH 2 groups are each optionally replaced by —O—, —S—, —C(═O)—, —C(═S)—, —C(═O)—O—, —O—C(═O)—, —NR 0 —, —C(═O)—NR 0 —, —NR 0 —C(═O)—, —SiR 0 R 00 —, —CF 2 —, —CHR 0 ═CR 00 —, —CY 1 ═CY 2 — 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 each optionally replaced by F, Cl, Br, I or CN,
Ar S1 and Ar S2 are independently of each other an aryl or heteroaryl group with 5 to 20 ring atoms, which is mono- or polycyclic, and which is substituted b

Assignees

• Merck Patent Gmbh
• Nano-C Inc

Inventors

• Blouin Nicolas
• Berny Stephane
• Jackson Edward A
• Richter Henning
• He Feng

Classifications

• C07D333/08 Primary

  Hydrogen atoms or radicals containing only hydrogen and carbon atoms · CPC title

• Y02E10/549

  Organic PV cells · CPC title

• C07C2604/00

  Fullerenes, e.g. C60 buckminsterfullerene or C70 · CPC title

• C07C13/62

  with more than three condensed rings · CPC title

• H10K30/50

  Photovoltaic [PV] devices · CPC title