Diketopyrrolopyrrole oligomers and compositions, comprising diketopyrrolopyrrole oligomers
The present invention relates to compositions, comprising (a) a compound of the formula (I), and (b) a polymeric material, to specific 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 compositions, or oligomers according to the invention are used in organic field effect transistors, organic photovoltaics (solar cells) and photodiodes.
1. A composition, comprising:
(a) a compound of the formula
and
(b) a polymeric material,
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
or have the meaning of R 5 ,
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* are optionally the same or different and are each independently selected from
hydrogen,
a C 1 -C 100 alkyl group which can optionally be substituted with C 1 -C 8 alkyl, C 1 -C 8 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—,
a C 2 -C 100 alkenyl group which can optionally be substituted with C 1 -C 8 alkyl, C 1 -C 8 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—,
a C 3 -C 100 alkinyl group which can optionally be substituted with C 1 -C 8 alkyl, C 1 -C 8 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—,
a C 3 -C 12 cycloalkyl group which can optionally be substituted with C 1 -C 8 alkyl, C 1 -C 8 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—,
a C 6 -C 24 aryl group which can optionally be substituted with C 1 -C 8 alkyl, C 1 -C 8 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,
a C 2 -C 20 heteroaryl group which can optionally be substituted with C 1 -C 8 alkyl, C 1 -C 8 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
—CO—C 1 -C 18 alkyl, —CO—C 5 -C 12 cycloalkyl, —COO—C 1 -C 18 alkyl;
R 3 is hydrogen, halogen, cyano, C 1 -C 25 alkyl, C 1 -C 25 alkyl which is substituted by E and/or interrupted by D,
COO—C 1 -C 18 alkyl, C 3 -C 12 cycloalkyl, C 3 -C 12 cycloalkyl, which is substituted by G, C 2 -C 18 alkenyl, C 2 -C 18 alkynyl, C 1 -C 18 thioalkoxy, 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, or has the meaning of R 5 , or R 6 ;
Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , Ar 6 and Ar 7 are each independently one of 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(═O)—, —C(═CR 14 R 15 )—,
R 10 and R 11 are each independently 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 each independently 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 each independently 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 each independently 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 8 alkyl group, or a tri(C 1 -C 8 alkyl)silyl group,
R 18 and R 19 are each independently 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 each independently hydrogen, C 1 -C 25 alkyl, C 2 -C 25 alkenyl, C 2 -C 25 alkyl which is interrupted by —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 are optionally both bonded via oxygen and/or sulfur to the (hetero)aromatic residue and which are optionally both have up to 4 carbon atoms,
R 30 to R 37 are each independently hydrogen, C 1 -C 25 alkyl, C 2 -C 25 alkenyl, C 2 -C 25 alkyl which is interrupted by —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 40 and R 41 are each independently hydrogen, C 1 -C 25 alkyl, C 2 -C 25 alkenyl, C 2 -C 25 alkyl which is interrupted by —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 are each independently 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, C 3 -C 12 cycloalkyl, C 3 -C 12 cycloalkyl, 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,
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, and
R 39 and R 39′ are each independently 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, if the polymeric material is a diketopyrrolopyrrole (DPP) polymer, a quotient of a weight average molecular weight of the DPP polymer and a molecular weight of the repeating unit of the polymer is at least 5.
2. The composition according to claim 1 , wherein the polymeric material b) is selected from the group consisting of
wherein n′ is from 10 to 1000 and polymers comprising diketopyrrolopyrrole (DPP) repeating units.
3. The composition according to claim 2 , wherein the polymeric material is a polymer of formula:
wherein
each R 101 and R 102 have the meaning of R 1 ;
each A 6 and A 7 is independently selected from optionally substituted aryl and heteroaryl groups;
each M is an optional, conjugated moiety;
s is a number from 1 to 4;
t is a number from 1 to 4;
u is a number that is at least 1;
v is a number from 0 to 20; and
n is a number that is at least 5.
4. The composition according to claim 1 , wherein the compound of formula I is a compound of formula
5. A compound of formula
wherein
q is 0, or 1,
A 1 and A 2 are independently of each other a group of formula
or have the meaning of R 5 ,
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* are optionally the same or different and are each independently selected from
hydrogen,
a C 1 -C 100 alkyl group which can optionally be substituted with C 1 -C 8 alkyl, C 1 -C 8 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—,
a C 2 -C 100 alkenyl group which can optionally be substituted with C 1 -C 8 alkyl, C 1 -C 8 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—,
a C 3 -C 100 alkinyl group which can optionally be substituted with C 1 -C 8 alkyl, C 1 -C 8 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—,
a C 3 -C 12 cycloalkyl group which can optionally be substituted with C 1 -C 8 alkyl, C 1 -C 8 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—,
a C 6 -C 24 aryl group which can optionally be substituted with C 1 -C 8 alkyl, C 1 -C 8 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,
a C 2 -C 20 heteroaryl group which can optionally be substituted with C 1 -C 8 alkyl, C 1 -C 8 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
—CO—C 1 -C 18 alkyl, —CO—C 5 -C 12 cycloalkyl, —COO—C 1 -C 18 alkyl;
R 3 is hydrogen, halogen, cyano, C 1 -C 25 alkyl, C 1 -C 25 alkyl which is substituted by E and/or interrupted by D,
COO—C 1 -C 18 alkyl, C 3 -C 12 cycloalkyl, C 3 -C 12 cycloalkyl, which is substituted by G, C 2 -C 18 alkenyl, C 2 -C 18 alkynyl, C 1 -C 18 thioalkoxy, 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, or has the meaning of R 5 , or R 6 ;
Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , Ar 6 and Ar 7 are each independently one of a bivalent group of formula
X is —O—, —S—, —NR 10 —, —Si(R′ 8 )(R 19 )—, —Ge(R 18 )(R 19 )—, —C(R 12 )(R 13 )—, —C(═O)—, —C(═CR 14 R 15 )—,
R 10 and R 11 are each independently 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 each independently 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 each independently 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 each independently 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 8 alkyl group, or a tri(C 1 -C 8 alkyl)silyl group,
R 18 and R 19 are each independently 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 each independently hydrogen, C 1 -C 25 alkyl, C 2 -C 25 alkenyl, C 2 -C 25 alkyl which is interrupted by —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 are optionally both bonded via oxygen and/or sulfur to the (hetero)aromatic residue and which are optionally both have up to 4 carbon atoms,
R 30 to R 37 are each independently hydrogen, C 1 -C 25 alkyl, C 2 -C 25 alkenyl, C 2 -C 25 alkyl
which is interrupted by —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 40 and R 41 are each independently hydrogen, C 1 -C 25 alkyl, C 2 -C 25 alkenyl, C 2 -C 25 alkyl which is interrupted by —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 are each independently 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, C 3 -C 12 cycloalkyl, C 3 -C 12 cycloalkyl, 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,
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, and
R 39 and R 39′ are each independently 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, if the polymeric material is a diketopyrrolopyrrole (DPP) polymer, a quotient of a weight average molecular weight of the DPP polymer and a molecular weight of the repeating unit of the polymer is at least 5,
with the proviso that compounds of formula
wherein R 103 is 2-hexyldecyl and y is 3, or 4, are excluded.
6. The compound according to claim 5 , which is a compound of formula
7. A compound of formula
wherein
A 1 and A 2 are independently of each other a group of formula
or R 5 ,
A 3 is 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′ and R 2′* are optionally the same or different and are each independently selected from
hydrogen,
a C 1 -C 100 alkyl group which can optionally be substituted with C 1 -C 8 alkyl, C 1 -C 8 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—,
a C 2 -C 100 alkenyl group which can optionally be substituted with C 1 -C 8 alkyl, C 1 -C 8 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—,
a C 3 -C 100 alkinyl group which can optionally be substituted with C 1 -C 8 alkyl, C 1 -C 8 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—,
a C 3 -C 12 cycloalkyl group which can optionally be substituted with C 1 -C 8 alkyl, C 1 -C 8 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—,
a C 6 -C 24 aryl group which can optionally be substituted with C 1 -C 8 alkyl, C 1 -C 8 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,
a C 2 -C 20 heteroaryl group which can optionally be substituted with C 1 -C 8 alkyl, C 1 -C 8 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
—CO—C 1 -C 18 alkyl, —CO—C 5 -C 12 cycloalkyl, —COO—C 1 -C 18 alkyl;
R 3 is hydrogen, halogen, cyano, C 1 -C 25 alkyl, C 1 -C 25 alkyl which is substituted by E and/or interrupted by D,
COO—C 1 -C 18 alkyl, C 3 -C 12 cycloalkyl, C 3 -C 12 cycloalkyl, which is substituted by G, C 2 -C 18 alkenyl, C 2 -C 18 alkynyl, C 1 -C 18 thioalkoxy, 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, or has the meaning of R 5 , or R 6 ;
Ar 1 , Ar 2 and Ar 3 are each independently one of a bivalent group of formula
Ar 4 , Ar 5 , Ar 6 and Ar 7 are each independently one of a bivalent group of formula
wherein
X is —O—, —S—, —NR 10 —, —Si(R 18 )(R 19 )—, —Ge(R 18 )(R 19 )—, —C(R 12 )(R 13 )—, —C(═O)—, —C(═CR 14 R 15 )—,
R 10 and R 11 are each independently 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 each independently 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 each independently 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 each independently 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 8 alkyl group, or a tri(C 1 -C 8 alkyl)silyl group,
R 18 and R 19 are each independently 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 each independently hydrogen, C 1 -C 25 alkyl, C 2 -C 25 alkenyl, C 2 -C 25 alkyl which is interrupted by —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 are optionally both bonded via oxygen and/or sulfur to the (hetero)aromatic residue and which are optionally both have up to 4 carbon atoms,
R 30 to R 37 are each independently hydrogen, C 1 -C 25 alkyl, C 2 -C 25 alkenyl, C 2 -C 25 alkyl which is interrupted by —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 40 and R 41 are each independently hydrogen, C 1 -C 25 alkyl, C 2 -C 25 alkenyl, C 2 -C 25 alkyl which is interrupted by —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 are each independently 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, C 3 -C 12 cycloalkyl, C 3 -C 12 cycloalkyl, 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,
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, and
R 39 and R 39′ are each independently 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, if the polymeric material is a diketopyrrolopyrrole (DPP) polymer, a quotient of a weight average molecular weight of the DPP polymer and a molecular weight of the repeating unit of the polymer is at least 5,
with the proviso that Ar 1 , Ar 4 , Ar 5 , or Ar 7 does not represent a six membered ring, which is attached directly to the diketopyrrolopyrrole moiety; and that
are excluded.
8. The compound according to claim 7 , which is a compound of formula
wherein
g is an integer of 1 to 4,
R 1 , R 2 , R 1* and R 2* are a C 1 -C 38 alkyl group and
Ar 5 is
wherein h is 1, 2, or 3,
wherein
Ar 5 , A 1 and A 2 are as defined above,
R 1 , R 2 , R 1* and R 2* are a C 1 -C 38 alkyl group, and
Ar 4 and Ar 6 are each independently one of
9. The compound according to claim 5 , wherein the compound is selected from the group consisting of:
10. A semiconductor device comprising the composition according to claim 1 .
11. The semiconductor device according to claim 10 , wherein the device is in the form of a diode, a photodiode, a sensor, an organic field effect transistor, a transistor for flexible displays, or a heterojunction solar cell.
12. The compound according to claim 5 , wherein the compound is suitable as a p-type transistor.
13. A process for preparation of
a compound of formula
wherein R 2 is R 1* , the process comprising:
(a) reacting in the presence of a strong base 2 moles of a compound of formula
wherein R 200 and R 200′ are independently of each other a C 1 -C 8 alkyl group, or a benzyl group with 1 mole of a di-nitrile compound of the formula
(b) and then alkylating the compound of formula
obtained in step (a) with a compound R 2 —X 16 , where X 16 is halogen, under basic conditions in a dry solvent;
or a compound of formula
the process comprising
(a) reacting (in the presence of a strong base) 2 mole of a disuccinate with 1 mole of a nitrile of the formula
and 2 mole of a nitrile of the formula
(b) reacting the compound of formula
obtained in step a) with a bromide of the formula R 1 —X 16 (X 16 is halogen) in the presence of a base in a solvent, wherein R 1 , R 1′ , R 2′ , A 1 , A 3 and A 4 are as defined above;
or
a process for the preparation of a compound of the formula
the process comprising
(a) reacting (in the presence of a strong base) 2 moles of a compound of formula
(R 200 and R 200′ are independently of each other a C 1 -C 8 alkyl group, or a benzyl group) with 1 mole of a di-nitrile compound of the formula
(b) reacting the compound of formula
obtained in step a) with a halogenide of the formula R 2 —X 16 (X 16 is halogen) in the presence of a suitable base in a suitable solvent,
wherein
A 1 and A 2 are independently of each other a group of formula
or have the meaning of R 5 ,
A 3 and A 4 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* are optionally the same or different and are each independently selected from
hydrogen,
a C 1 -C 100 alkyl group which can optionally be substituted with C 1 -C 8 alkyl, C 1 -C 8 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—,
a C 2 -C 100 alkenyl group which can optionally be substituted with C 1 -C 8 alkyl, C 1 -C 8 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—,
a C 3 -C 100 alkinyl group which can optionally be substituted with C 1 -C 8 alkyl, C 1 -C 8 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—,
a C 3 -C 12 cycloalkyl group which can optionally be substituted with C 1 -C 8 alkyl, C 1 -C 8 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—,
a C 6 -C 24 aryl group which can optionally be substituted with C 1 -C 8 alkyl, C 1 -C 8 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,
a C 2 -C 20 heteroaryl group which can optionally be substituted with C 1 -C 8 alkyl, C 1 -C 8 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
—CO—C 1 -C 18 alkyl, —CO—C 5 -C 12 cycloalkyl, —COO—C 1 -C 18 alkyl;
R 3 is hydrogen, halogen, cyano, C 1 -C 25 alkyl, C 1 -C 25 alkyl which is substituted by E and/or interrupted by D,
COO—C 1 -C 18 alkyl, C 3 -C 12 cycloalkyl, C 3 -C 12 cycloalkyl, which is substituted by G, C 2 -C 18 alkenyl, C 2 -C 18 alkynyl, C 1 -C 18 thioalkoxy, 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, or has the meaning of R 5 , or R 6 ;
Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , Ar 6 and Ar 7 are each independently one of 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(═O)—, —C(═CR 14 R 15 )—,
R 10 and R 11 are each independently 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 each independently 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 each independently 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 each independently 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 8 alkyl group, or a tri(C 1 -C 8 alkyl)silyl group,
R 18 and R 19 are each independently 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 each independently hydrogen, C 1 -C 25 alkyl, C 2 -C 25 alkenyl, C 2 -C 25 alkyl which is interrupted by —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 are optionally both bonded via oxygen and/or sulfur to the (hetero)aromatic residue and which are optionally both have up to 4 carbon atoms,
R 30 to R 37 are each independently hydrogen, C 1 -C 25 alkyl, C 2 -C 25 alkenyl, C 2 -C 25 alkyl which is interrupted by —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 40 and R 41 are each independently hydrogen, C 1 -C 25 alkyl, C 2 -C 25 alkenyl, C 2 -C 25 alkyl which is interrupted by —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 are each independently 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, C 3 -C 12 cycloalkyl, C 3 -C 12 cycloalkyl, 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,
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, and
R 39 and R 39′ are each independently 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, if the polymeric material is a diketopyrrolopyrrole (DPP) polymer, a quotient of a weight average molecular weight of the DPP polymer and a molecular weight of the repeating unit of the polymer is at least 5.
14. A compound of formula
wherein
A 1′ and A 2′ are independently of each other a group of formula
R 3′ is independently in each occurrence ZnX 12 , —SnR 207 R 208 R 209 , wherein R 207 , R 208 and R 209 are identical or different and are H or C 1 -C 6 alkyl, wherein two radicals optionally form a common ring and these radicals are optionally branched or unbranched;
X 12 is a halogen atom; —OS(O) 2 CF 3 , —OS(O) 2 -aryl, —OS(O) 2 CH 3 , —B(OH) 2 , —B(OH) 3 − , —BF 3 , —B(OY 1 ) 2 ,
Y 1 is independently in each occurrence a C 1 -C 8 alkyl group and
Y 2 is independently in each occurrence a C 2 -C 10 alkylene group, and
Y 13 and Y 14 are each independently hydrogen, or a C 1 -C 8 alkyl group
p is 0, or 1,
q is 0, or 1,
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* are optionally the same or different and are each independently selected from
hydrogen,
a C 1 -C 100 alkyl group which can optionally be substituted with C 1 -C 8 alkyl, C 1 -C 8 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—,
a C 2 -C 100 alkenyl group which can optionally be substituted with C 1 -C 8 alkyl, C 1 -C 8 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—,
a C 3 -C 100 alkinyl group which can optionally be substituted with C 1 -C 8 alkyl, C 1 -C 8 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—,
a C 3 -C 12 cycloalkyl group which can optionally be substituted with C 1 -C 8 alkyl, C 1 -C 8 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—,
a C 6 -C 24 aryl group which can optionally be substituted with C 1 -C 8 alkyl, C 1 -C 8 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,
a C 2 -C 20 heteroaryl group which can optionally be substituted with C 1 -C 8 alkyl, C 1 -C 8 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
—CO—C 1 -C 18 alkyl, —CO—C 5 -C 12 cycloalkyl, —COO—C 1 -C 18 alkyl;
R 3 is hydrogen, halogen, cyano, C 1 -C 25 alkyl, C 1 -C 25 alkyl which is substituted by E and/or interrupted by D,
COO—C 1 -C 18 alkyl, C 3 -C 12 cycloalkyl, C 3 -C 12 cycloalkyl, which is substituted by G, C 2 -C 18 alkenyl, C 2 -C 18 alkynyl, C 1 -C 18 thioalkoxy, 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, or has the meaning of R 5 , or R 6 ;
Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , Ar 6 and Ar 7 are each independently one of 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(═O)—, —C(═CR 14 R 15 )—,
R 10 and R 11 are each independently 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 each independently 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 each independently 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 each independently 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 8 alkyl group, or a tri(C 1 -C 8 alkyl)silyl group,
R 18 and R 19 are each independently 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 each independently hydrogen, C 1 -C 25 alkyl, C 2 -C 25 alkenyl, C 2 -C 25 alkyl which is interrupted by —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 are optionally both bonded via oxygen and/or sulfur to the (hetero)aromatic residue and which are optionally both have up to 4 carbon atoms,
R 30 to R 37 are each independently hydrogen, C 1 -C 25 alkyl, C 2 -C 25 alkenyl, C 2 -C 25 alkyl which is interrupted by —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 40 and R 41 are each independently hydrogen, C 1 -C 25 alkyl, C 2 -C 25 alkenyl, C 2 -C 25 alkyl which is interrupted by —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 are each independently 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, C 3 -C 12 cycloalkyl, C 3 -C 12 cycloalkyl, 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,
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, and
R 39 and R 39′ are each independently 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, if the polymeric material is a diketopyrrolopyrrole (DPP) polymer, a quotient of a weight average molecular weight of the DPP polymer and a molecular weight of the repeating unit of the polymer is at least 5.
15. A process for the preparation of a polymer comprising repeating unit(s) of formula
the process comprising polymerizing the compound of formula (X) according to claim 14 as an intermediate, wherein A 1″ and A 2″ are independently of each other a group of formula
16. The composition of claim 1 , wherein:
R 3 is hydrogen, halogen, cyano, C 1 -C 25 alkyl, C 1 -C 25 alkyl which is substituted by E and/or interrupted by D, COO—C 1 -C 18 alkyl, C 3 -C 12 cycloalkyl, C 3 -C 12 cycloalkyl, which is substituted by G, C 2 -C 18 alkenyl, C 2 -C 18 alkynyl, C 1 -C 18 thioalkoxy, 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, or has the meaning of R 5 , or R 6 ; and
Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , Ar 6 and Ar 7 are each independently one of a bivalent group of formula
17. The compound of claim 5 , wherein:
R 3 is hydrogen, halogen, cyano, C 1 -C 25 alkyl, C 1 -C 25 alkyl which is substituted by E and/or interrupted by D, COO—C 1 -C 18 alkyl, C 3 -C 12 cycloalkyl, C 3 -C 12 cycloalkyl, which is substituted by G, C 2 -C 18 alkenyl, C 2 -C 18 alkynyl, C 1 -C 18 thioalkoxy, 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, or has the meaning of R 5 , or R 6 ; and
Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , Ar 6 and Ar 7 are each independently one of a bivalent group of formula
18. The compound of claim 7 , wherein:
R 3 is hydrogen, halogen, cyano, C 1 -C 25 alkyl, C 1 -C 25 alkyl which is substituted by E and/or interrupted by D, COO—C 1 -C 18 alkyl, C 3 -C 12 cycloalkyl, C 3 -C 12 cycloalkyl, which is substituted by G, C 2 -C 18 alkenyl, C 2 -C 18 alkynyl, C 1 -C 18 thioalkoxy, 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, or has the meaning of R 5 , or R 6 ;
Ar 1 , Ar 2 and Ar 3 are each independently one of a bivalent group of formula
and
Ar 4 , Ar y , Ar 6 and Ar 7 are each independently one of a bivalent group of formula
19. The process of claim 13 , wherein:
R 3 is hydrogen, halogen, cyano, C 1 -C 25 alkyl, C 1 -C 25 alkyl which is substituted by E and/or interrupted by D, COO—C 1 -C 18 alkyl, C 3 -C 12 cycloalkyl, C 3 -C 12 cycloalkyl, which is substituted by G, C 2 -C 18 alkenyl, C 2 -C 18 alkynyl, C 1 -C 18 thioalkoxy, 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, or has the meaning of R 5 , or R 6 ; and
Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , Ar 6 and Ar 7 are each independently one of a bivalent group of formula
20. The compound of claim 14 , wherein:
R 3 is hydrogen, halogen, cyano, C 1 -C 25 alkyl, C 1 -C 25 alkyl which is substituted by E and/or interrupted by D, COO—C 1 -C 18 alkyl, C 3 -C 12 cycloalkyl, C 3 -C 12 cycloalkyl, which is substituted by G, C 2 -C 18 alkenyl, C 2 -C 18 alkynyl, C 1 -C 18 thioalkoxy, 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, or has the meaning of R 5 , or R 6 ; and
Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , Ar 6 and Ar 7 are each independently one of a bivalent group of formula