Pyrrolopyrrole derivatives, their manufacture and use
The present invention relates to compounds of the formula (I) wherein the substituents are as defined in claim 1 , and their use as organic semiconductor in organic devices, like diodes, organic field effect transistors and/or a solar cells. The compounds of the formula I have excellent solubility in organic solvents. High efficiency of energy conversion, excellent field-effect mobility, good on/off current ratios and/or excellent stability can be observed, when said compounds are used in semiconductor devices or organic photovoltaic (PV) devices (solar cells).
1. A compound of the formula I
wherein R 1 and R 2 are independently of each other an aliphatic, cycloaliphatic, cycloaliphatic-aliphatic, aromatic, aromatic-aliphatic, heteroaromatic or heteroaromatic-aliphatic group having up to 49 carbon atoms,
a and d independently of each other are 0, 1, 2 or 3,
Ar 1 and Ar 4 are independently of each other a bivalent group of the formula II or IV
wherein
R 6 and R 7 are as defined below,
p represents 0, 1, or 2,
R 5 is an aliphatic hydrocarbon group having up to 25 carbon atoms, or two vicinal groups R 5 together represent alkylene or alkenylene having up to 7 carbon atoms, it being possible that two groups R 5 present in the group of formula II differ from each other,
b, c, e, and f independently of each other represent 1, 2 or 3,
Ar 2 , Ar 3 , Ar 5 , and Ar 6 are independently of each other a bivalent group of one of the formulae IV to X,
wherein R 6 , R 7 , R 8 , R 9 , R 12 , R 13 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 and R 21 are independently of each other hydrogen, C 1 -C 25 alkyl, C 1 -C 18 alkoxy, C 6 -C 24 aryl, C 7 -C 25 aralkyl, or heteroaryl, or R 6 and R 7 together represent alkylene or alkenylene which may be both bonded via oxygen and/or sulfur to the thienyl residue and which may both have up to 25 carbon atoms,
R 10 and R 11 are independently of each other hydrogen, C 1 -C 18 alkyl, C 6 -C 24 aryl, heteroaryl, or R 10 and R 11 together represent oxo or form a five or six membered ring, which is unsubstituted or substituted by
a) an aliphatic hydrocarbon group having up to 18 carbon atoms,
b) C 1 -C 18 alkoxy or C 2 -C 18 alkylenedioxy in both of which carbon atoms which are not adjacent to oxygen may be replaced by oxygen, or
c) C 6 -C 24 aryl, C 7 -C 25 aralkyl, heteroaryl, C 3 -C 12 cycloalkyl or C 4 -C 12 cycloalkyl-alkyl, and R 3 and R 4 are independently of each other a group of one of the formulae,
(XIV)
wherein R 22 to R 26 and R 29 to R 58 represent independently of each other hydrogen, an aliphatic hydrocarbon group having up to 25 carbon atoms, alkoxy or alkenyloxy having up to 18 carbon atoms, halogen, a cycloaliphatic, cycloaliphatic-aliphatic, aromatic, aromatic-aliphatic, heteroaromatic or heteroaromatic-aliphatic group having up to 25 carbon atoms, or a group of the formula (III)
wherein R represents an aliphatic hydrocarbon group having up to 12 carbon atoms, or two groups R 22 to R 26 and R 29 to R 57 which are in the neighborhood of each other, together represent alkylene or alkenylene having up to 8 carbon atoms, thereby forming a ring, and R 27 and R 28 are independently of each other hydrogen, C 1 -C 25 alkyl, C 1 -C 18 alkoxy, C 6 -C 24 aryl, C 7 -C 25 aralkyl, heteroaryl, or a group of the formula (III) shown above, wherein R represents an aliphatic hydrocarbon group having up to 12 carbon atoms, or R 27 and R 28 together or R 27 and R 58 together represent alkylene or alkenylene which may be both bonded via oxygen and/or sulfur to the thienyl residue and which may both have up to 25 carbon atoms.
2. A compound of the formula I according to claim 1 wherein R 1 and R 2 are independently of each other an aliphatic, cycloaliphatic, cycloaliphatic-aliphatic, aromatic, aromatic-aliphatic, heteroaromatic or heteroaromatic-aliphatic group having up to 25 carbon atoms, R 3 and R 4 are independently of each other a group of one of the formulae
wherein R 22 to R 26 and R 29 to R 58 represent independently of each other hydrogen, an aliphatic hydrocarbon group having up to 25 carbon atoms, or a group of the formula (III)
wherein R represents an aliphatic hydrocarbon group having up to 12 carbon atoms, or two groups R 22 to R 26 and R 29 to R 57 which are in the neighborhood of each other, together represent alkylene or alkenylene having up to 8 carbon atoms, thereby forming a ring, and
R 27 and R 28 are independently of each other hydrogen, C 1 -C 25 alkyl, C 1 -C 18 alkoxy, C 6 -C 24 aryl, C 7 -C 25 aralkyl, heteroaryl, or a group of the formula (III) shown above, wherein R represents an aliphatic hydrocarbon group having up to 12 carbon atoms, or R 27 and R 28 together or R 27 and R 58 together represent alkylene or alkenylene which may be both bonded via oxygen and/or sulfur to the thienyl residue and which may both have up to 25 carbon atoms, and the remaining substituents are as defined in claim 1 .
3. A compound of the formula I according to claim 1 wherein R 1 and R 2 are independently of each other an aliphatic, cycloaliphatic or cycloaliphatic-aliphatic hydrocarbon group having up to 25 carbon atoms,
a and d represent 0,
b, c, e, and f represent 1,
Ar 2 , Ar 3 , Ar 5 , and Ar 6 are independently of each other a bivalent group of the formula IV,
wherein R 6 and R 7 are independently of each other hydrogen or C 1 -C 25 alkyl, and
R 3 and R 4 are independently of each other a group of the formula
wherein R 58 represents hydrogen or an aliphatic hydrocarbon group having up to 25 carbon atoms, and
R 27 and R 28 are independently of each other hydrogen or C 1 -C 25 alkyl.
4. A compound of the formula I according to claim 1 wherein R 1 and R 2 are independently of each other an aliphatic, cycloaliphatic or cycloaliphatic-aliphatic hydrocarbon group having up to 25 carbon atoms,
a and d represent 0,
b, c, e, and f represent 1,
Ar 2 and Ar 5 are independently of each other a bivalent group of the formula IV,
wherein one of R 6 and R 7 represents C 1 -C 25 alkyl while the other of R 6 and R 7 represents hydrogen or C 1 -C 25 alkyl,
Ar 3 and Ar 6 are a bivalent group of the formula IV, wherein each of R 6 and R 7 represents hydrogen, and
R 3 and R 4 are independently of each other a group of the formula
wherein R 58 represents hydrogen or an aliphatic hydrocarbon group having up to 25 carbon atoms, and
one of R 27 and R 28 represents C 1 -C 25 alkyl while the other of R 27 and R 28 represents hydrogen or C 1 C 25 alkyl.
5. A compound of the formula I according to claim 1 wherein R 1 and R 2 are independently of each other an alkyl group having up to 49 carbon atoms,
a and d are independently of each other 0, 1 or 2,
Ar 1 and Ar 4 are independently of each other a bivalent group of the formula IV
wherein
R 6 and R 7 are independently of each other hydrogen or C 1 -C 25 alkyl,
b, c, e, and f independently of each other represent 1, 2 or 3
Ar 2 , Ar 3 , Ar 5 , and Ar 6 are independently of each other a bivalent group of the formula IV,
wherein R 6 and R 7 are independently of each other hydrogen, C 1 -C 25 alkyl, or C 7 -C 25 aralkyl, and
R 3 and R 4 are independently of each other a group of one of the formulae
wherein R 22 to R 26 , R 29 to R 33 , R 41 to R 55 , R 57 and R 58 represent independently of each other hydrogen, an aliphatic hydrocarbon group having up to 25 carbon atoms, aryl, alkoxy having up to 18 carbon atoms, or halogen, or two groups R 22 to R 26 which are in the neighborhood of each other, together represent alkylene or alkenylene having up to 8 carbon atoms, thereby forming a ring, and R 27 and R 28 are independently of each other hydrogen, C 1 -C 25 alkyl, or C 7 -C 25 aralkyl, or R 27 and R 28 together represent alkylene or alkenylene which may be both bonded via oxygen and/or sulfur to the thienyl residue and which may both have up to 25 carbon atoms.
6. A compound of the formula I according to claim 1 wherein R 1 and R 2 have the same meaning and the side chains of the formulae XLV and XLVI are identical to each other
7. A compound of the formula I according to claim 1 selected from the compounds having the following formulae
8. A compound of the formula I according to claim 1 selected from the compounds having the following formulae