Thienothiophene-isoindigo

1. A polymer, comprising:

at least one unit of formula (1)

wherein

X 1 , X 2 and X 3 are independently from each other S or NR 1 ,

A is

wherein

X 4 is S or NR 1 , and

A1 can be substituted with one substituent R 2 ,

B is selected from the group consisting of

wherein

X 5 and X 6 are independently from each other S or NR 1 , and

B1, B2 and B3 can be substituted with one to three substituents R 2 ,

R 1 is at each occurrence selected from the group consisting of C 1-50 -alkyl, C 2-50 -alkenyl and C 2-50 -alkynyl,

wherein

C 1-50 -alkyl, C 2-50 -alkenyl and C 2-50 -alkynyl can be substituted with one to twenty substituents independently selected from the group consisting of C 5-6 -cycloalkyl, C 6-10 -aryl, 5 to 10 membered heteroaryl, OR a , SR a ,

Si(R Sia )(R Sib )(R Sic ), —O—Si(R Sia )(R Sib )(R Sic ), halogen, and CN; and at least two CH 2 -groups, but not adjacent CH 2 -groups, of C 1-50 -alkyl, C 2-50 -alkenyl and C 2-50 -alkynyl can be replaced by O or S,

wherein

R a is independently selected from the group consisting of H, C 1-30 -alkyl, C 2-30 -alkenyl, C 2-30 -alkynyl, C 5-6 -cycloalkyl and C 6-10 -aryl,

R Sia , R Sib and R Sic are independently selected from the group consisting of H, C 1-30 -alkyl, C 2-30 -alkenyl, C 2-30 -alkynyl, C 5-6 -cycloalkyl, C 6-10 -aryl, —[O—SiR Sid R Sie ] o —R Sif ,

wherein

o is an integer from 1 to 50,

R Sid , R Sie , R Sif are independently selected from the group consisting of H, C 1-30 -alkyl, C 2-30 -alkenyl, C 2-30 -alkynyl, C 5-6 -cycloalkyl, C 6-10 -aryl, —[O—SiR Sig R Sih ] p —R Sii ,

wherein

p is an integer from 1 to 50,

R Sig R Sih , R Sii are independently selected from the group consisting of H, C 1-30 -alkyl, C 2-30 -alkenyl, C 2-30 -alkynyl, C 5-6 -cycloalkyl, C 6-10 -aryl, O—Si(CH 3 ) 3 ,

and

R 2 is at each occurrence selected from the group consisting of unsubstituted C 1-30 -alkyl and halogen,

n is 0, 1, 2 or 3,

m is 0, 1, 2 or 3,

and

L 1 and are L 2 are independently from each other and at each occurrence selected from the group consisting of C 6-18 -arylene, 5 to 20 membered heteroarylene,

wherein

C 6-18 -arylene and 5 to 20 membered heteroarylene can be substituted with one to six substituents R 3 at each occurrence selected from the group consisting of C 1-30 -alkyl, C 2-30 -alkenyl, C 2-30 -alkynyl, C 5-12 -cycloalkyl, C 6-18 -aryl and 5 to 20 membered heteroaryl, OR 31 , OC(O)—R 31 , C(O)—OR 31 , C(O)—R 31 , NR 31 R 32 , NR 31 —C(O)—R 32 , C(O)—NR 31 R 32 , N[C(O)R 31 ][C(O)R 32 ], SR 31 , halogen, CN, SiR Siv R Siw R Six and OH, and

wherein

can be substituted with one or two substituents R 4 at each occurrence selected from the group consisting of C 1-30 -alkyl, C 2-30 -alkenyl, C 2-30 -alkynyl, C 5-12 -cycloalkyl, C 6-18 -aryl and 5 to 20 membered heteroaryl, C(O)—R 41 , C(O)—NR 41 R 42 , C(O)—OR 41 and CN,

wherein

R 31 , R 32 , R 41 and R 42 are independently from each other and at each occurrence selected from the group consisting of H, C 1-30 -alkyl, C 2-30 -alkenyl, C 2-30 -alkynyl, C 5-12 -cycloalkyl, C 6-18 -aryl and 5 to 20 membered heteroaryl, and

wherein

C 1-30 -alkyl, C 2-30 -alkenyl and C 2-30 -alkynyl can be substituted with one to ten substituents independently selected from the group consisting of C 5-8 -cycloalkyl, C 6-14 -aryl, 5 to 14 membered heteroaryl, OR i , OC(O)—R j , C(O)—OR i , C(O)—R i , NR i R j , NR i —C(O)R j , C(O)—NR i R j , N[C(O)R i ][C(O)R j ], SR i , halogen, CN, SiR Siv R Siw R Six and NO 2 ; and at least two CH 2 -groups, but not adjacent CH 2 -groups of C 1-30 -alkyl, C 2-30 -alkenyl and C 2-30 -alkynyl can be replaced by O or S,

C 5-12 -cycloalkyl can be substituted with one to six substituents independently selected from the group consisting of C 1-20 -alkyl, C 2-20 -alkenyl and C 2-20 -alkynyl, C 5-8 -cycloalkyl, C 6-14 -aryl, 5 to 14 membered heteroaryl, OR i , OC(O)—R j , C(O)—OR i , C(O)—R i , NR i R j , NR i —C(O)R j , C(O)—NR i R j , N[C(O)R i ][C(O)R j ], SR i , halogen, CN, SiR Siv R Siw R Six and NO 2 ; and one or two CH 2 -groups, but not adjacent CH 2 -groups, of C 5-12 -cycloalkyl can be replaced by O, S, OC(O), CO, NR i or NR i —CO, C 6-18 -aryl and 5 to 20 membered heteroaryl can be substituted with one to six substituents independently selected from the group consisting of C 1-20 -alkyl, C 2-20 -alkenyl, C 2-20 -alkynyl, C 5-8 -cycloalkyl, C 6-14 -aryl, 5 to 14 membered heteroaryl, OR i , OC(O)—R j , C(O)—OR i , C(O)—R i , NR i R j , NR i —C(O)R j , C(O)—NR i R j , N[C(O)R i ][C(O)R j ], SR i , halogen, CN, SiR Siv R Siw R Six and NO 2 ,

wherein

R Siv , R Siw , and R Six are independently from each other selected from the group consisting of H, C 1-20 -alkyl, C 2-20 -alkenyl, C 2-20 -alkynyl, C 5-6 -cycloalkyl, phenyl and O—Si(CH 3 ) 3 ,

R i and R j are independently selected from the group consisting of H, C 1-20 -alkyl, C 2-20 -alkenyl, C 2-20 -alkynyl, C 5-8 -cycloalkyl, C 6-14 -aryl, and 5 to 14 membered heteroaryl,

wherein

C 1-20 -alkyl, C 2-20 -alkenyl and C 2-20 -alkynyl can be substituted with one to five substituents selected from the group consisting of C 5-6 -cycloalkyl, C 6-10 -aryl, 5 to 10 membered heteroaryl, OR k , OC(O)—R l , C(O)—OR k , C(O)—R k , NR k R l , NR k -C(O)R l , C(O)—NR k R l , N[C(O)R k ][C(O)R l ], SR k , halogen, CN, and NO 2 ;

C 5-8 -cycloalkyl can be substituted with one to five substituents selected from the group consisting of C 1-10 -alkyl, C 2-10 -alkenyl, C 2-10 -alkynyl, C 5-6 -cycloalkyl, C 6-10 -aryl, 5 to 10 membered heteroaryl, OR k , OC(O)—R l , C(O)—OR k , C(O)—R k , NR k R l , NR k —C(O)R l , C(O)—NR k R l , N[C(O)R k ][C(O)R l ], SR k , halogen, CN, and NO 2 ;

C 6-14 -aryl and 5 to 14 membered heteroaryl can be substituted with one to five substituents independently selected from the group consisting of C 1-10 -alkyl, C 2-10 -alkenyl, C 2-10 -alkynyl, C 5 -6 -cycloalkyl, C 6-10 -aryl, 5 to 10 membered heteroaryl, OR k , OC(O)—R l , C(O)—OR k , C(O)—R k , NR k R l , NR k —C(O)R l , C(O)—NR k R l , N[C(O)R k ][C(O)R l ], SR k , halogen, CN, and NO 2 ;

 wherein

 R k and R l are independently selected from the group consisting of H, C 1-10 -alkyl, C 2-10 -alkenyl and C 2-10 -alkynyl,

 wherein

 C 1-10 -alkyl, C 2-10 -alkenyl and C 2-10 -alkynyl can be substituted with one to five substituents selected from the group consisting of halogen, CN and NO 2 .

2. The polymer of claim 1 , wherein

X 1 is S, and X 2 and X 3 are NR 1 .

3. The polymer of claim 1 , wherein

A is

wherein

X 4 is S or NR 1 , and

A1 can be substituted with one substituent R 2 ,

B is

wherein

X 5 and X 6 are independently from each other S or NR 1 , and

B2 can be substituted with one substituent R 2 ,

R 1 is at each occurrence selected from the group consisting of C 1-36 -alkyl, C 2-36 -alkenyl and C 2-36 -alkynyl,

wherein

C 1-36 -alkyl, C 2-36 -alkenyl and C 2-36 -alkynyl can be substituted with one to twenty substituents independently selected from the group consisting of C 5-6 -cycloalkyl, C 6-10 -aryl, 5 to 10 membered heteroaryl, OR a , SR a ,

Si(R Sia )(R Sib )(R Sic ), —O—Si(R Sia )(R Sib )(R Sic ), halogen, and CN; and at least two CH 2 -groups, but not adjacent CH 2 -groups, of C 1-36 -alkyl, C 2-36 -alkenyl and C 2-36 -alkynyl can be replaced by O or S,

wherein

R a is selected from the group consisting of H, C 1-20 -alkyl, C 2-20 -alkenyl, C 2-20 -alkynyl, C 5-6 -cycloalkyl and C 6-10 -aryl

R Sia , R Sib and R Sic are independently selected from the group consisting of H, C 1-20 -alkyl, C 2-20 -alkenyl, C 2-20 -alkynyl, C 5-6 -cycloalkyl, C 6-10 -aryl, —[O—SiR Sid R Sic ] o —R Sif

wherein

o is an integer from 1 to 50,

R Sid , R Sie , R Sif are independently selected from the group consisting of H, C 1-30 -alkyl, C 2-20 -alkenyl, C 2-20 -alkynyl, C 5-6 -cycloalkyl, C 6-10 -aryl, —[O—SiR Sig R Sih ] p —R Sii ,

 wherein

 p is an integer from 1 to 50,

 R Sig R Sih , R Sii are independently selected from the group consisting of H, C 1-30 -alkyl, C 2-20 -alkenyl, C 2-20 -alkynyl, C 5-6 -cycloalkyl, C 6-10 -aryl, O—Si(CH 3 ) 3 ,

and

R 2 is at each occurrence selected from the group consisting of unsubstituted C 1-30 -alkyl and halogen.

4. The polymer of claim 1 , wherein

A is

wherein

X 4 is S and

A1 is not substituted,

B is

wherein

X 5 and X 6 are S, and

B2 is not substituted, and

R 1 is at each occurrence unsubstituted C 1-36 -alkyl.

5. The polymer of claim 1 , wherein

L 1 and L 2 are independently from each other and at each occurrence selected from the group consisting of 5 to 20 membered heteroarylene,

and

wherein

5 to 20 membered heteroarylene can be substituted with one to six substituents R 3 at each occurrence selected from the group consisting of C 1-30 -alkyl, C 2-30 -alkenyl, C 2-30 -alkynyl, C 5-12 -cycloalkyl, C 6-18 -aryl and 5 to 20 membered heteroaryl, OR 31 , OC(O)—R 31 , C(O)—OR 31 , C(O)—R 31 , NR 31 R 32 , NR 31 —C(O)R 32 , C(O)—NR 31 R 32 , SR 31 , halogen, CN, SiR Siv R Siw R Six and OH, and

wherein

can be substituted with one or two substituents R 4 at each occurrence selected from the group consisting of C 1-30 -alkyl, C 2-30 -alkenyl, C 2-30 -alkynyl, C 5-12 -cycloalkyl, C 6-18 -aryl and 5 to 20 membered heteroaryl, C(O)—R 41 , C(O)—NR 41 R 42 , C(O)—OR 41 and CN,

wherein

R 31 , R 32 , R 41 and R 42 are independently from each other and at each occurrence selected from the group consisting of H, C 2-30 -alkenyl, C 2-30 -alkynyl, C 5-12 -cycloalkyl, C 6-18 -aryl and 5 to 20 membered heteroaryl, and

wherein

C 1-30 -alkyl, C 2-30 -alkenyl and C 2-30 -alkynyl can be substituted with one to ten substituents independently selected from the group consisting of C 5-8 -cycloalkyl, C 6-14 -aryl, 5 to 14 membered heteroaryl, OR i , OC(O)—R j , C(O)—OR i , C(O)—R i , NR i R j , NR i —C(O)R j , C(O)—NR i R j , N[C(O)R i ][C(O)R j ], SR i , halogen, CN, SiR Siv R Siw R Six and NO 2 ; and at least two CH 2 -groups, but not adjacent CH 2 -groups of C 1-30 -alkyl, C 2-30 -alkenyl and C 2-30 -alkynyl can be replaced by O or S,

C 5-12 -cycloalkyl can be substituted with one to six substituents independently selected from the group consisting of C 1-20 -alkyl, C 2-20 -alkenyl and C 2-20 -alkynyl, C 5-8 -cycloalkyl, C 6-14 -aryl, 5 to 14 membered heteroaryl, OR i , OC(O)—R j , C(O)—OR i , C(O)—NR i R j , NR i —C(O)R j , C(O)—NR i R j , N[C(O)R i ][C(O)R j ], SR i , halogen, CN, SiR Siv R Siw R Six and NO 2 ; and one or two CH 2 -groups, but not adjacent CH 2 -groups, of C 5-12 -cycloalkyl can be replaced by O, S, OC(O), CO, NR i or NR i —CO,

C 6-18 -aryl and 5 to 20 membered heteroaryl can be substituted with one to six substituents independently selected from the group consisting of C 1-20 -alkyl, C 2-20 -alkenyl, C 2-20 -alkynyl, C 5-8 -cycloalkyl, C 6-14 -aryl, 5 to 14 membered heteroaryl, OR i , OC(O)—R j , C(O)—OR i , C(O)—R i , NR i R j , NR i —C(O)R j , C(O)—NR i R j , N[C(O)R i ][C(O)R j ], SR i , halogen, CN, SiR Siv R Siw R Six and NO 2 ,

wherein

R Siv , R Siw , and R Six are independently from each other selected from the group consisting of

H, C 1-20 -alkyl, C 2-20 -alkenyl, C 2-20 -alkynyl, C 5-6 -cycloalkyl, phenyl and O—Si(CH 3 ) 3 , R i and R j are independently selected from the group consisting of H, C 1-20 -alkyl, C 2-20 -alkenyl, C 2-20 -alkynyl, C 5-8 -cycloalkyl, C 6-14 -aryl, and 5 to 14 membered heteroaryl,

wherein

C 1-20 -alkyl, C 2-20 -alkenyl and C 2-20 -alkynyl can be substituted with one to five substituents selected from the group consisting of C 5-6 -cycloalkyl, C 6-10 -aryl, 5 to 10 membered heteroaryl, OR k , OC(O)—R l , C(O)—OR k , C(O)—R k , NR k R l , NR k —C(O)R l , C(O)—NR k R l , N[C(O)R k ][C(O)R l ], SR k , halogen, CN, and NO 2 ;

C 5-8 -cycloalkyl can be substituted with one to five substituents selected from the group consisting of C 1-10 -alkyl, C 2-10 -alkenyl, C 2-10 -alkynyl, C 5-6 -cycloalkyl, C 6-10 -aryl, 5 to 10 membered heteroaryl, OR k , OC(O)—R l , C(O)—OR k , C(O)—R k , NR k R l , NR k —C(O)R l , C(O)—NR k R l , N[C(O)R k ][C(O)R l ], SR k , halogen, CN, and NO 2 ;

C 6-14 -aryl and 5 to 14 membered heteroaryl can be substituted with one to five substituents independently selected from the group consisting of C 1-10 -alkyl, C 2-10 -alkenyl, C 2-10 -alkynyl, C 5-6 -cycloalkyl, C 6-10 -aryl, 5 to 10 membered heteroaryl, OR k , OC(O)—R l , C(O)—OR k , C(O)—R k , NR k R l , NR k —C(O)R l , C(O)—NR k R l , N[C(O)R k ][C(O)R l ], SR k , halogen, CN, and NO 2 ;

wherein

R k and R l are independently selected from the group consisting of H, C 1-10 -alkyl, C 2-10 -alkenyl and C 2-10 -alkynyl, and

 wherein

 C 1-10 -alkyl, C 2-10 -alkenyl and C 2-10 -alkynyl can be substituted with one to five substituents selected from the group consisting of halogen, CN and NO 2 .

6. The polymer of claim 1 , wherein

L 1 and L 2 are independently from each other and at each occurrence selected from the group consisting of 5 to 20 membered heteroarylene,

and

wherein 5 to 20 membered heteroarylene is selected from the group consisting of

wherein

R 104 and R 105 are independently and at each occurrence selected from the group consisting of H, C 1-20 -alkyl, C 2-20 -alkenyl, C 2-20 -alkynyl, C 5-8 -cycloalkyl, C 6-14 -aryl, and 5 to 14 membered heteroaryl, or R 104 and R 105 , if attached to the same atom, together with the atom, to which they are attached, form a 5 to 12 membered ring system,

wherein

C 1-20 -alkyl, C 2-20 -alkenyl and C 2-20 -alkynyl can be substituted with one to five substituents selected from the group consisting of C 5-6 -cycloalkyl, C 6-10 -aryl, 5 to 10 membered heteroaryl, OR s , OC(O)—R t , C(O)—OR s , C(O)—R s , NR s R t , NR s —C(O)R t , C(O)—NR s R t , N[C(O)R s ][C(O)R t ], SR s , halogen, CN, and NO 2 ;

C 5-8 -cycloalkyl can be substituted with one to five substituents selected from the group consisting of C 1-10 -alkyl, C 2-10 -alkenyl, C 2-10 -alkynyl, C 5-6 -cycloalkyl, C 6-10 -aryl, 5 to 10 membered heteroaryl, OR s , OC(O)—R t , C(O)—OR s , C(O)—R s , NR s R t , NR s —C(O)R t , C(O)—NR s R t , N[C(O)R s ][C(O)R t ], SR s , halogen, CN, and NO 2 ;

C 6-14 -aryl and 5 to 14 membered heteroaryl can be substituted with one to five substituents independently selected from the group consisting of C 1-10 -alkyl, C 2-10 -alkenyl, C 2-10 -alkynyl, C 5-6 -cycloalkyl, C 6-10 -aryl, 5 to 10 membered heteroaryl, OR s , OC(O)—R t , C(O)—OR s , C(O)—R s , NR s R t , NR s —C(O)R t , C(O)—NR s R t , N[C(O)R s ][C(O)R t ], SR s , halogen, CN, and NO 2 ;

5 to 12 membered ring system can be substituted with one to five substituents selected from the group consisting of C 1-10 -alkyl, C 2-10 -alkenyl, C 2-10 -alkynyl, C 5-6 -cycloalkyl, C 6-10 -aryl, 5 to 10 membered heteroaryl, OR s , OC(O)—R t , C(O)—OR s , C(O)—R s , NR s R t , NR s —C(O)R t , C(O)—NR s R t , N[C(O)R s ][C(O)R t ], SR s , halogen, CN, and NO 2 ;

wherein

R s and R t are independently selected from the group consisting of H, C 1-10 -alkyl, C 2-10 -alkenyl and C 2-10 -alkynyl,

wherein

C 1-10 -alkyl, C 2-10 -alkenyl and C 2-10 -alkynyl can be substituted with one to five substituents selected from the group consisting of halogen, CN and NO 2 ,

wherein

5 to 20 membered heteroarylene can be substituted with one to six substituents R 3 at each occurrence selected from the group consisting of C 1-30 -alkyl and halogen, and

wherein

can be substituted with one or two substituents R 4 at each occurrence selected from the group consisting of C 1-30 -alkyl, C(O)—R 41 , C(O)—OR 41 and CN, and

wherein

R 41 is at each occurrence C 1-30 -alkyl.

7. The polymer of claim 1 , wherein

L 1 and L 2 are independently from each other and at each occurrence 5 to 20 membered heteroarylene,

wherein 5 to 20 membered heteroarylene is selected from the group consisting of

wherein

5 to 20 membered heteroarylene is unsubstituted.

8. The polymer of claim 5 , wherein

n is 0, 1 or 2, and

m is 0, 1 or 2.

9. A process for the preparation of the polymer of claim 1 , wherein n is 0 and which are of formula (1-I)

which process comprises:

treating a compound of formula (2)

wherein Y is at each occurrence I, Br, Cl or O—S(O) 2 CF 3 , and X 1 , X 2 , X 3 , A and B are as defined for the compound of formula (1)

with m mol equivalents of a compound of formula (3)

Z a -L 2 -Z b   (3)

wherein

L 2 is as defined for the compound of formula (1), and

Z a and Z b are independently selected from the group consisting of B(OZ 1 )(OZ 2 ), SnZ 1 Z 2 Z 3 ,

wherein Z 1 , Z 2 , Z 3 , Z 4 , Z 5 and Z 6 are independently from each other and at each occurrence H or C 1-4 -alkyl.

10. An electronic device, comprising:

a polymer of claim 1 .

11. The electronic device of claim 10 , wherein the electronic device is an organic field effect transistor.

12. A method of making a semiconductor, the method comprising:

depositing a polymer according to claim 1 onto a substrate.

13. A method of transmitting electrons within a semiconductor material, the method comprising:

passing electrons through a polymer according to claim 1 , said polymer comprised within a semiconductor device.