Diketopyrrolopyrrole oligomers for use in organic semiconductor devices
The present invention relates to oligomers of the formula (I), and their use as organic semiconductor in organic devices, especially in organic photovoltaics (solar cells) and photodiodes, or in a device containing a diode and/or an organic field effect transistor. High efficiency of energy conversion, excellent field-effect mobility, good on/off current ratios and/or excellent stability can be observed, when the oligomers according to the invention are used in organic field effect transistors, organic photovoltaics (solar cells) and photodiodes.
1. A compound of formula (I)
wherein
p is 0, or 1, q is 0, or 1,
A 1 and A 2 are independently of each other a group of formula
A 3 , A 4 and A 5 are independently of each other a group of formula
a is 1 or 2; b is 0, 1 or 2; c is 0, 1 or 2;
k is 0, 1, or 2; l is 1, 2, or 3; r is 0, or 1; z is 0, 1 or 2;
R 1 , R 2 , R 1′ , R 2′ , R 1″ , R 2″ , R 1* and R 2* may be the same or different and are a C 1 -C 100 alkyl group which can optionally be substituted one or more times with C 1 -C 12 alkyl, C 1 -C 12 alkoxy, halogen, C 5 -C 12 cycloalkyl, nitro, cyano, vinyl, allyl, C 6 -C 24 aryl, C 2 -C 20 heteroaryl, a silyl group or a siloxanyl group and/or can optionally be interrupted by —O—, —S—, —NR 39 —, —COO—, —CO— or —OCO;
R 3 is hydrogen,
Ar 1 is
and Ar 2 , Ar 3 , Ar 4 , Ar 5 , Ar 6 and Ar 7 are independently of each other a bivalent group of formula
X is —O—, —S—, —NR 10 —, —Si(R 18 )(R 19 )—, —Ge(R 18 )(R 19 )—, —C(R 12 )(R 13 )—, —C(═CR 14 R 15 ),
R 10 and R 11 are independently of each other hydrogen, C 1 -C 18 alkyl, C 1 -C 18 haloalkyl, C 7 -C 25 arylalkyl, or C 1 -C 18 alkanoyl,
R 12 and R 13 are independently of each other hydrogen, C 1 -C 18 alkyl, C 1 -C 18 haloalkyl, C 7 -C 25 arylalkyl, C 6 -C 24 aryl, or C 2 -C 20 heteroaryl, or R 12 and R 13 together represent oxo,
or form a five or six membered ring, which is unsubstituted or substituted by C 1 -C 18 alkyl and/or C 1 -C 18 alkoxy;
R 14 and R 15 are independently of each other hydrogen, C 1 -C 18 alkyl, C 6 -C 24 aryl, C 2 -C 20 heteroaryl, —CN or COOR 50 ;
R 16 and R 17 are independently of each other hydrogen, halogen, C 1 -C 25 alkyl, C 1 -C 25 alkoxy, C 7 -C 25 arylalkyl, or
R x is a C 1 -C 12 alkyl group, or a tri(C 1 -C 8 alkyl)silyl group,
R 18 and R 19 are independently of each other hydrogen, C 1 -C 18 alkyl, C 7 -C 25 arylalkyl, or a phenyl group, which optionally can be substituted one to three times with C 1 -C 8 alkyl and/or C 1 -C 8 alkoxy,
R 20 and R 21 are independently of each other hydrogen, C 1 -C 25 alkyl, C 2 -C 25 alkenyl, C 2 -C 25 alkyl which is interrupted by one or more —O— or —S—, COOR 50 , cyano, C 1 -C 18 alkoxy, C 6 -C 24 aryl, C 7 -C 25 arylalkyl, halogen or C 2 -C 20 heteroaryl, or R 20 and R 21 together represent alkylene or alkenylene which may be both bonded via oxygen and/or sulfur to the (hetero)aromatic residue and which may both have up to 4 carbon atoms,
R 30 to R 37 are independently of each other hydrogen, C 1 -C 25 alkyl, C 2 -C 25 alkenyl, C 2 -C 25 alkyl which is interrupted by one or more —O— or —S—, COOR 50 , cyano, C 1 -C 25 alkoxy, C 6 -C 24 aryl, C 7 -C 25 arylalkyl, halogen or C 2 -C 20 heteroaryl,
R 40 and R 41 are independently of each other hydrogen, C 1 -C 25 alkyl, C 2 -C 25 alkenyl, C 2 -C 25 alkyl which is interrupted by one or more —O— or —S—, COOR 50 , cyano, C 1 -C 18 alkoxy, C 6 -C 24 aryl, C 7 -C 25 arylalkyl, halogen or C 2 -C 20 heteroaryl,
R 50 is C 1 -C 25 alkyl, C 1 -C 25 haloalkyl, C 7 -C 25 arylalkyl, C 6 -C 24 aryl or C 2 -C 20 heteroaryl;
R 60 to R 68 represent independently of each other H, halogen, cyano, C 1 -C 25 alkyl, C 1 -C 25 alkyl which is substituted by E and/or interrupted by D, C 6 -C 24 aryl, C 6 -C 24 aryl which is substituted by G, C 2 -C 20 heteroaryl, C 2 -C 20 heteroaryl which is substituted by G, a C 4 -C 18 cycloalkyl group, a C 4 -C 18 cycloalkyl group, which is substituted by G, C 2 -C 18 alkenyl, C 2 -C 18 alkynyl, C 1 -C 18 alkoxy, C 1 -C 18 alkoxy which is substituted by E and/or interrupted by D, C 7 -C 25 aralkyl, or C 7 -C 25 aralkyl, which is substituted by G,
R 70 and R 71 are independently of each other hydrogen, C 1 -C 25 alkyl, or C 7 -C 25 aralkyl, or R 70 and R 71 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,
D is —CO—, —COO—, —S—, —O—, —NR 39 —, or —C(═O)NR 39 —,
E is C 1 -C 8 thioalkoxy, COO—C 1 -C 18 alkyl, C 1 -C 8 alkoxy, CN, —NR 39 R 39′ , —CONR 39 R 39″ , or halogen,
G is E, or C 1 -C 18 alkyl,
R 39 and R 39′ are independently of each other hydrogen, C 1 -C 18 alkyl, C 1 -C 18 haloalkyl, C 7 -C 25 arylalkyl, or C 1 -C 18 alkanoyl,
with the proviso that Ar 5 is different from a group
if q is 0, p is 0, k is 0, r is 0, z is 0 and l is 1.
2. The compound according to claim 1 of formula (Ia), (Ib) or (Ic)
3. The compound according to claim 1 , wherein R 1 , R 2 , R 1′ , R 2′ , R 1″ , R 2″ , R 1* and R 2* may be the same or different and are C 1 -C 50 alkyl, C 1 -C 50 haloalkyl, C 7 -C 25 arylalkyl.
4. The compound according to claim 1 , wherein
A 1 and A 2 are independently of each other a group of Formula
wherein
a is 1, b is 0, or 1, c is 0, or 1,
Ar 2 and Ar 3 are independently of each other a group of formula
R 10 is a hydrogen, C 1 -C 25 alkyl or COO—C 1 -C 25 alkyl,
R 16 and R 17 are independently of each other hydrogen, halogen, C 1 -C 25 alkyl, C 1 -C 25 alkoxy, C 7 -C 25 arylalkyl, or
R X is a C 1 -C 12 alkyl group, or a tri (C 1 -C 8 alkyl)silyl group,
R 20 and R 21 are independently of each other hydrogen, or C 1 -C 25 alkyl,
R 30 to R 35 are independently of each other hydrogen, or C 1 -C 25 alkyl,
R 42 and R 43 are independently of each other C 1 -C 25 alkyl; and
R 3 is hydrogen.
5. The compound according to claim 4 , wherein
A 1 and A 2 are independently of each other a group of formula
wherein
a is 1, b is 0, or 1, c is 0, or 1,
Ar 2 and A 3 are independently of each other
and R 3 is H.
6. The compound according to claim 1 , wherein
A 3 , A 4 and A 5 are independently of each other a group of formula
k is 0, 1, or 2; l is 1, 2, or 3; r is 0, or 1; z is 0, 1 or 2;
Ar 4 , Ar 5 , Ar 6 and Ar 7 are independently of each other a group of formula
R 10 is hydrogen, C 1 -C 25 alkyl or COO—C 1 -C 25 alkyl,
R 16 and R 17 are independently of each other hydrogen, halogen, C 1 -C 25 alkyl, C 1 -C 25 alkoxy,
C 7 -C 25 arylalkyl, or
R X is a C 1 -C 25 alkyl group, or a tri(C 1 -C 8 alkyl)silyl group,
R 20 and R 21 are independently of each other hydrogen, or C 1 -C 25 alkyl,
R 30 to R 35 are independently of each other hydrogen, or C 1 -C 25 alkyl, and
R 42 and R 43 are independently of each other C 1 -C 25 alkyl.
7. The compound according to claim 5 , wherein A 3 , A 4 and A 5 are independently of each other a group of formula
k and z are 0, or 1; l is 1, 2, or 3; r is 0;
Ar 4 and Ar 7 are a group of formula
Ar 5 is a group of formula
y is 1, 2 or 3,
R 10 is H, or C 1 -C 25 alkyl,
R 16 and R 17 are H, or C 1 -C 25 alkyl, and
R 32 and R 33 are H, or C 1 -C 25 alkoxy.
8. The compound according to claim 1 of formula (IIa), (IIb), (IIc), (IIIa), (IIIb) or (IIIc),
wherein
b is 0, or 1, c is 0, or 1,
A 3 , A 4 , Ar 5 and Ar 6 are independently of each other a group of formula
y is 1, 2, or 3,
Ar 2 and Ar 3 are independently of each other
R 1 , R 2 , R 1′ , R 2′ , R 1* and R 2* are C 1 -C 50 alkyl, C 1 -C 50 haloalkyl, C 7 -C 25 arylalkyl
R 3 is H,
R 10 is H, or C 1 -C 25 alkyl,
R 16 and R 17 are H, or C 1 -C 25 alkyl, and
R 32 and R 33 are H, or C 1 -C 25 alkoxy.
9. A compound of formula (A-1)-(A22), (B-1) or (B-2)
10. A semiconductor device comprising a compound of the formula I as defined in claim 1 .
11. A semiconductor device according to claim 10 in the form of a diode, a photodiode, a sensor, an organic field effect transistor, a transistor for flexible displays, or a solar cell.
12. The compound according to claim 2 wherein R 1 , R 2 , R 1′ , R 2′ , R 1″ , R 2″ , R 1* and R 2* may be the same or different and are C 1 -C 50 alkyl, C 1 -C 50 haloalkyl, C 7 -C 25 arylalkyl.
13. The compound according to claim 2 , wherein A 1 and A 2 are independently of each other a group of formula
wherein
a is 1, b is 0, or 1, c is 0, or 1,
Ar 2 and Ar 3 are independently of each other a group of formula
R 10 is hydrogen, C 1 -C 25 alkyl or COO—C 1 -C 25 alkyl,
R 16 and R 17 are independently of each other hydrogen, halogen, C 1 -C 25 alkyl, C 1 -C 25 alkoxy, C 7 -C 25 arylalkyl, or
R X is a C 1 -C 12 alkyl group, or a tri(C 1 -C 8 alkyl)silyl group,
R 20 and R 21 are independently of each other hydrogen, or C 1 -C 25 alkyl,
R 30 to R 35 are independently of each other hydrogen, or C 1 -C 25 alkyl,
R 42 and R 43 are independently of each other C 1 -C 25 alkyl; and
R 3 is hydrogen.
14. The compound according to claim 12 , wherein
A 1 and A 2 are independently of each other a group of formula
wherein
a is 1, b is 0, or 1, c is 0, or 1,
Ar 2 and Ar 3 are independently of each other a group of formula
R 10 is hydrogen, C 1 -C 25 alkyl or COO—C 1 -C 25 alkyl,
R 16 and R 17 are independently of each other hydrogen, halogen, C 1 -C 25 alkyl, C 1 -C 25 alkoxy, C 7 -C 25 arylalkyl, or
R X is a C 1 -C 25 alkyl group, or a tri(C 1 -C 8 alkyl)silyl group,
R 20 and R 21 are independently of each other hydrogen, or C 1 -C 25 alkyl,
R 30 to R 35 are independently of each other hydrogen, or C 1 -C 25 alkyl,
R 42 and R 43 are independently of each other C 1 -C 25 alkyl; and
R 3 is hydrogen.
15. The compound according to claim 14 , wherein
A 1 and A 2 are independently of each other a group of formula
wherein
a is 1, b is 0, or 1, c is 0, or 1,
Ar 2 is,
and R 3 is H.
16. The compound according to claim 15 , wherein
A 3 , A 4 and A 5 are independently of each other a group of formula
k is 0, 1, or 2; l is 1, 2, or 3; r is 0, or 1; z is 0, 1 or 2;
Ar 4 , Ar 5 , Ar 6 and Ar 7 are independently of each other a group of formula
R 10 is hydrogen, C 1 -C 25 alkyl or COO—C 1 -C 25 alkyl,
R 16 and R 17 are independently of each other hydrogen, halogen, C 1 -C 25 alkyl, C 1 -C 25 alkoxy, C 7 -C 25 arylalkyl, or
R X is a C 1 -C 12 alkyl group, or a tri(C 1 -C 8 alkyl)silyl group,
R 20 and R 21 are independently of each other hydrogen, or C 1 -C 25 alkyl,
R 30 to R 35 are independently of each other hydrogen, or C 1 -C 25 alkyl, and
R 42 and R 43 are independently of each other C 1 -C 25 alkyl.
17. The compound according to claim 15 , wherein A 3 , A 4 , and A 5 are independently of each other a group of formula
k and z are 0, or 1; 1 is 1, 2, or 3; r is 0;
Ar 4 and Ar 7 are a group of formula
Ar 5 is a group of formula
y is 1, 2, or 3,
R 10 is H, or C 1 -C 25 alkyl,
R 16 and R 17 are H, or C 1 -C 25 alkyl, and
R 32 and R 33 are H, or C 1 -C 25 alkoxy.
18. The compound according to claim 17 of formula (IIa), (IIb), (IIc), (IIIa), (IIIb) or (IIIc),
wherein
b is 0, or 1, c is 0, or 1,
A 3 , A 4 , Ar 5 and Ar 6 are independently of each other a group of formula
y is 1, 2, or 3,
Ar 2 and Ar 3 are independently of each other
R 1 , R 2 , R 1′ , R 2′ , R 1″ , R 2″ , R 1* and R 2* are selected from hydrogen, C 1 -C 50 alkyl, C 1 -C 50 haloalkyl, C 7 -C 25 arylalkyl, C 2 -C 50 alkenyl, C 2 -C 50 haloalkenyl, allyl, C 5 -C 12 cycloalkyl, phenyl, or naphthyl which can optionally be substituted one or more times with C 1 -C 12 alkyl or C 1 -C 12 alkoxy, —O—C 1 -C 18 alkyl, —CO—C 5 -C 12 cycloalkyl and —COO—C 1 -C 18 alkyl,
R 3 is H,
R 10 is H, or C 1 -C 25 alkyl,
R 16 and R 17 are H, or C 1 -C 25 alkyl, and
R 32 and R 33 are H, or C 1 -C 25 alkoxy.