Carbazolocarbazol-bis(dicarboximides) and their use as semiconductors

Patent metadata

Field	Value
Publication number	US-9583719-B2
Application number	US-201214238382-A
Country	US
Kind code	B2
Filing date	Aug 10, 2012
Priority date	Aug 12, 2011
Publication date	Feb 28, 2017
Grant date	Feb 28, 2017

Abstract

The present invention relates to carbazolocarbazol-bis(dicarboximides), a method for their preparation and their use as semiconductors, in particular as semiconductors in organic electronics and organic photovoltaics.

First claim

The invention claimed is:

1. A compound of formula I

wherein
R 1 , R 2 , R 3 , and R 4 are each independently selected from the group consisting of hydrogen and an unsubstituted or a substituted alkyl, cycloalkyl, heterocycloalkyl, aryl and hetaryl group,
R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are each independently selected from the group consisting of
hydrogen,
an unsubstituted or a substituted alkyl, alkoxy, alkylthio, (monoalkyl)amino, (dialkyl)amino, cycloalkyl, cycloalkoxy, cycloalkylthio, (monocycloalkyl)amino, (dicycloalkyl)amino, heterocycloalkyl, heterocycloalkoxy, heterocycloalkylthio, (monoheterocycloalkyl)amino, (diheterocycloalkyl)amino, aryl, aryloxy, arylthio, (monoaryl)amino, (diaryl)amino, hetaryl, hetaryloxy, hetarylthio, (monohetaryl)amino, (dihetaryl)amino group,
a halogen atom, a hydroxy group, a mercapto group, a cyano group, a nitro group, a cyanato group, a thiocyanato group, a formyl group, an acyl group, a carboxy group, a carboxylate group, an alkylcarbonyloxy group, a carbamoyl group, an alkylaminocarbonyl group, a dialkylaminocarbonyl group, a sulfo group, a sulfonate group, a sulfoamino group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, an amidino group, and a NE 1 E 2 group, where E 1 and E 2 are each independently hydrogen, an alkyl group, a cycloalkyl group, a heterocycloalkyl group, an aryl group or a hetaryl group, and
in each case at least two adjacent radicals from R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 , together with the carbon atoms of the benzene ring to which R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are bonded, optionally form a fused ring system comprising 1, 2, 3, 4, 5, 6, 7 or 8 further rings.

2. The compound according to claim 1 , wherein at least one of R 1 , R 2 , R 3 and R 4 is selected from the group consisting of A.1-A.16 shown as follows:

wherein
# is a bonding side to a nitrogen atom,
A C 1 -C 10 -alkylene group which is optionally interrupted by one or more nonadjacent groups selected from the group consisting of —O— and —S—,
y is 0 or 1,
R h in A.5, A.8, A.11 and A.14 are each independently a C 1 -C 30 -alkyl group, a C 1 -C 30 -fluoroalkyl group, fluorine, chlorine, bromine, a nitro group, a cyano group, or a NE 1 E 2 group, where E 1 and E 2 are independently hydrogen, an alkyl group, a cycloalkyl group, a heterocycloalkyl group, an aryl group or a hetaryl group,
R i in A.6, A.7, A.9, A.10, A.12, A.13, A.15 and A.16 are each independently a C 1 -C 30 -alkyl group,
x in A.5, A.6 and A.7 is 1, 2, 3, 4 or 5,
x in A.8, A.9 and A.10 is 1, 2, 3 or 4,
x in A.11, A.12 and A.13 is 1, 2 or 3, and
x in A.14, A.15 and A.16 is 1 or 2.

3. The compound according to claim 1 , wherein at least one of R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 is selected from the group consisting of B.1-B.16 shown as follows:

wherein
# is a bonding side to a nitrogen atom,
B is a divalent bridging group selected from the group consisting of —O—, —S— or C 1 -C 10 -alkylene which optionally interrupted or terminated by one or more nonadjacent groups of —O— or —S—,
q is 0 or 1,
R e in B.5, B.8, B.11 and B.14 are each independently a C 1 -C 30 -alkyl group, a C 1 -C 30 -fluoroalkyl group, fluorine, chlorine, bromine, a nitro group, a cyano group, or a NE 1 E 2 group, where E 1 and E 2 are each independently hydrogen, an alkyl group, a cycloalkyl group, a heterocycloalkyl group, an aryl group or a hetaryl group,
R f in B.6, B.7, B.9, B.10, B.12, B.13, B.15 and B.16 are each independently a C 1 -C 30 -alkyl group,
p in B.5, B.6 and B.7 is 1, 2, 3, 4 or 5,
p in B.8, B.9 and B.10 is 1, 2, 3 or 4,
p in B.11, B.12 and B.13 is 1, 2 or 3, and
p in B.14, B.15 and B.16 is 1 or 2.

4. A compound according to claim 1 , wherein at least one of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 is a linear C 1 -C 30 -alkyl radical or a branched C 3 -C 30 -alkyl radical.

5. The compound according to claim 1 , wherein
at least one of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 is a radical of formula (C)

# is a bonding site,
m is 0 or 1, and
R d and R e are each independently a C 1 - to C 30 -alkyl group.

6. The compound according to claim 1 , wherein
at least one of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 is a radical of formula (C1)

# is a bonding site,
R d and R e are each independently a C 1 - to C 28 -alkyl group, and
a sum of carbon atoms of R d and R e is an integer of from 2 to 29.

7. The compound according to claim 1 , wherein at least one of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 is a perfluoro-C 1 -C 30 -alkyl group, a 1H,1H-perfluoro-C 2 -C 30 -alkyl group or a 1H,1H,2H,2H-perfluoro-C 3 -C 30 -alkyl group.

8. The compound according to claim 1 , wherein R 1 and R 2 are the same.

9. The compound according to claim 1 , wherein R 3 and R 4 are the same.

10. The compound according to claim 1 , wherein R 1 and R 2 are both 2,6-diisopropylphenyl.

11. The compound according to claim 1 , wherein R 3 and R 4 are both hydrogen.

12. The compound according to claim 1 , wherein
R 5 is the same as R 9 ,
R 6 is the same as R 10 ,
R 7 is the same as R 11 , and
R 8 is the same as R 12 .

13. The compound according to claim 1 , wherein R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are all hydrogen.

14. The compound according to claim 1 , wherein
R 5 , R 6 , R 8 , R 9 , R 10 and R 12 are all hydrogen, and
R 7 and R 11 are Cl.

15. The compound according to claim 1 , wherein
R 5 , R 6 , R 8 , R 9 , R 10 and R 12 are all hydrogen, and
R 7 and R 11 are F.

16. The compound according to claim 1 , wherein
R 5 , R 6 , R 8 , R 9 , R 10 and R 12 are all hydrogen, and
R 7 and R 11 are Br.

17. The compound according to claim 1 , wherein
R 5 , R 6 , R 8 , R 9 , R 10 and R 12 are all hydrogen, and
R 7 and R 11 are CN.

18. The compound according to claim 1 , wherein
R 5 , R 7 , R 9 and R 11 are hydrogen, and
R 6 , R 8 , R 10 and R 12 are CF 3 .

19. A process for preparing the compound according to claim 1 , the process comprising:
reacting a 2,6-dibromonaphthalene-1,4,5,8-tetracarboxylic acid bisimide of formula (II)
with a compound of formula (IIIa) and, optionally, a different compound of formula (IIIb):

wherein
R 1 and R 2 are each independently selected

Assignees

• Suraru Sabin-Lucian
• WüRTHNER FRANK
• Geβner Thomas
• Basf Se

Inventors

• Suraru Sabin-Lucian
• WüRTHNER FRANK
• Geβner Thomas

Classifications

• C07D471/22

  in which the condensed systems contains four or more hetero rings · CPC title

• Y02E10/549

  Organic PV cells · CPC title

• C09K11/06 Primary

  containing organic luminescent materials · CPC title

• H05B33/10

  Apparatus or processes specially adapted to the manufacture of electroluminescent light sources · CPC title

• C09K2211/1029

  containing one nitrogen atom as the heteroatom · CPC title