Semiconducting materials based on naphthalenediimide-vinylene-oligothiophene-vinylene polymers

1. A polymer comprising a unit of formula

wherein

R 1 and R 2 are independently from each other C 1-30 -alkyl, C 2-30 -alkenyl, C 2-30 -alkynyl, phenyl or a 5 to 8 membered heterocyclic ring system,

wherein each of the C 1-30 -alkyl, C 2-30 -alkenyl or C 2-30 -alkynyl group may be substituted with 1 to 10 substituents independently selected from the group consisting of halogen, —CN, —NO 2 , —OH, —NH 2 , —NH(C 1-20 -alkyl), —N(C 1-20 -alkyl) 2 , —NH—C(O)—(C 1-20 -alkyl), —S(O) 2 OH, —CHO, —C(O)—C 1-20 -alkyl, —C(O)OH, —C(O)—OC 1-20 -alkyl, —C(O)NH 2 , —CO(O)NH—C 1-20 -alkyl, —C(O)N(C 1-20 -alkyl) 2 , —O—C 1-20 -alkyl, —O—C(O)—C 1-20 -alkyl, —SiH 3 , SiH 2 (C 1-20 -alkyl), SiH(C 1-20 -alkyl) 2 , Si(C 1-20 -alkyl) 3 , C 4-8 -cycloalkyl, phenyl and a 5 to 8 membered heterocyclic ring system, and

phenyl or a 5 to 8 membered heterocyclic ring system may be substituted with 1 to 5 C 1-16 -alkyl groups,

o is 2 or 3

and

n is an integer from 2 to 10,000.

2. The polymer of claim 1 , wherein

R 1 and R 2 are independently from each other C 6-30 -alkyl, C 6-30 -alkenyl, C 6-30 -alkynyl, or phenyl, wherein each of the C 6-30 -alkyl, C 6-30 -alkenyl or C 6-30 -alkynyl groups may be substituted with 1 to 10 substituents independently selected from the group consisting of halogen, —CN, —NO 2 , —OH, —NH 2 , —NH(C 1-20 -alkyl), —N(C 1-20 -alkyl) 2 , —NH—C(O)—(C 1-20 -alkyl), —S(O) 2 OH, —CHO, —C(O)—C 1-20 -alkyl, —C(O)OH, —C(O)—OC 1-20 -alkyl, —C(O)NH 2 , —CO(O)NH—C 1-20 -alkyl, —C(O)N(C 1-20 -alkyl) 2 , —O—C 1-20 -alkyl, and N—O—C(O)—C 1-20 -alkyl, and phenyl may be substituted with 1 or 2 C 1-16 -alkyl groups.

3. The polymer of claim 1 , wherein

R 1 and R 2 are independently from each other C 6-30 -alkyl, C 6-30 -alkenyl or C 6-30 -alkynyl,

wherein each of the C 6-30 -alkyl, C 6-30 -alkenyl or C 6-30 -alkynyl group may be substituted with 1 to 10 substituents independently selected from the group consisting of halogen, —CN, —NO 2 , —NH(C 1-20 -alkyl), —N(C 1-20 -alkyl) 2 , —NH—C(O)—(C 1-20 -alkyl), —C(O)—C 1-20 -alkyl, —C(O)—OC 1-20 -alkyl, —C(O)NH 2 , —CO(O)NH—C 1-20 -alkyl, —C(O)N(C 1-20 -alkyl) 2 , —O—C 1-20 -alkyl, and N—O—C(O)—C 1-20 -alkyl.

4. The polymer of claim 1 , wherein

R 1 and R 2 are independently from each other C 6-30 -alkyl,

wherein each of the C 6-30 -alkyl may be substituted with 1 to 10 substituents independently selected from the group consisting of halogen, —CN, —NO 2 , —NH(C 1-20 -alkyl), —N(C 1-20 -alkyl) 2 , —NH—C(O)—(C 1-20 -alkyl), —C(O)—C 1-20 -alkyl, —C(O)—OC 1-20 -alkyl, —C(O)NH 2 , —CO(O)NH—C 1-20 -alkyl, —C(O)N(C 1-20 -alkyl) 2 , —O—C 1-20 -alkyl, and N—O—C(O)—C 1-20 -alkyl.

5. The polymer of claim 1 , wherein R 1 and R 2 are independently from each other C 10-30 -alkyl.

6. The polymer of claim 5 , wherein R 1 and/or R 2 are independently from each other 2-octyldodecyl.

7. The polymer of claim 1 , wherein o is 2.

8. The polymer of claim 1 , wherein n is an integer from 5 to 1,000.

9. The polymer of claim 1 , wherein n is an integer from 5 to 500.

10. The polymer of claim 1 , wherein n is an integer from 10 to 100.

11. The polymer of claim 1 comprising a unit of formula

wherein n is an integer from 20 to 100.

12. An electronic device comprising the polymer of claim 1 as semiconducting material.

13. The electronic device of claim 12 , wherein the electronic device is an organic field effect transistor.

14. The electronic device of claim 12 , wherein the electronic device is an organic photovoltaic device.

15. A semiconducting material comprising the polymer of claim 1 .

16. A process for the preparation of the polymer of claim 1 , comprising reacting a compound of formula

wherein

R 1 and R 2 are independently from each other C 1-30 -alkyl, C 2-30 -alkenyl, C 2-30 -alkynyl, phenyl or a 5 to 8 membered heterocyclic ring system,

wherein each of the C 1-30 -alkyl, C 2-30 -alkenyl or C 2-30 -alkynyl group may be substituted with 1 to 10 substituents independently selected from the group consisting of halogen, —CN, —NO 2 , —OH, —NH 2 , —NH(C 1-20 -alkyl), —N(C 1-20 -alkyl) 2 , —NH—C(O)—(C 1-20 -alkyl), —S(O) 2 OH, —CHO, —C(O)—C 1-20 -alkyl, —C(O)OH, —C(O)—OC 1-20 -alkyl, —C(O)NH 2 , —CO(O)NH—C 1-20 -alkyl, —C(O)N(C 1-20 -alkyl) 2 , —O—C 1-20 -alkyl, —O—C(O)—C 1-20 -alkyl, —SiH 3 , SiH 2 (C 1-20 -alkyl), SiH(C 1-20 -alkyl), Si(C 1-20 -alkyl) 3 , C 4-8 -cycloalkyl, phenyl and a 5 to 8 membered heterocyclic ring system, and

phenyl and the 5 to 8 membered heterocyclic ring system may be substituted with 1 to 5 C 1-16 -alkyl groups, and

X is triflate or halogen,

with a compound of formula

wherein

R 3 and R 4 are independently from each other H or C 1-10 -alkyl, or R 3 and R 4 together with the —O—B—O— unit linking them form a cycle which may be substituted with one or two C1-6-alkyl,

M is an alkali metal, an alkaline earth metal or Al,

m is 1, 2 or 3,

o is 2 or 3.

17. The process of claim 16 , wherein X is Br.

18. The process of claim 16 , wherein R 3 and R 4 together with the —O—B—O— unit linking them form a five-membered cycle.

19. The process of claim 16 , wherein R 3 and R 4 together with the —O—B—O— unit linking them form a five-membered cycle, which is substituted with one or two C1-6-alkyl.

20. The process of claim 19 , wherein the five-membered cycle is substituted with one or two methyl.