Photoactive polymers

1. An article, comprising:

a first electrode,

a second electrode, and

a photoactive layer disposed between the first and second electrodes, the photoactive layer comprising a polymer including a first monomer repeat unit, the first monomer repeat unit comprising a moiety of formula (1):

in which A is S; and R is H, C 1 -C 24 alkyl optionally containing oxygen, C 2 -C 24 alkenyl, C 2 -C 24 alkynyl, C 3 -C 24 cycloalkyl, C 3 -C 24 cycloalkenyl, C 3 -C 24 heterocycloalkyl, C 3 -C 24 heterocycloalkenyl, aryl, or heteroaryl;

wherein the article is configured as a photovoltaic cell.

2. The article of claim 1 , wherein R is C 1 -C 24 alkyl optionally containing oxygen and optionally substituted with halo or C 1 -C 24 alkoxy.

3. The article of claim 2 , wherein R is C 8 H 17 , C 12 H 25 , or C 20 H 41 .

4. The article of claim 1 , wherein the polymer further comprises a second monomer repeat unit different from the first monomer repeat unit.

5. The article of claim 4 , wherein the second monomer repeat unit comprises a moiety selected from the group consisting of the moieties of formulas (2)-(23):

wherein

each X, independently, is O, S, or Se;

each Y, independently, is N or C(R a );

Z 1 is N(R a ), S, Si(R a R b ), or C(R a R b );

Z 2 is O, S, Se, N(R a ), Si(R a R b ), or C(R a R b );

Z 3 is O, S, or N(R a );

each Z 4 , independently, is CH 2 , O, or S;

each of R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 , independently, is H, halo, C 1 -C 24 alkyl, C 2 -C 24 alkenyl, C 2 -C 24 alkynyl, C 3 - C 24 cycloalkyl, C 3 -C 24 cycloalkenyl, C 3 -C 24 heterocycloalkyl, C 3 - C 24 heterocycloalkenyl, aryl, heteroaryl, OR c , COR c , or COOR c ;

R 7 is H, C 1 -C 24 alkyl, C 2 -C 24 alkenyl, C 2 -C 24 alkynyl, C 3 -C 24 cycloalkyl, C 3 - C 24 cycloalkenyl, C 3 -C 24 heterocycloalkyl, C 3 -C 24 heterocycloalkenyl, aryl, heteroaryl, COR c or COOR c ;

each R a , independently, is H, halo, C 1 -C 24 alkyl, aryl, heteroaryl, C 3 -C 24 cycloalkyl, or C 3 -C 24 heterocycloalkyl;

each R b , independently, is H, halo, C 1 -C 24 alkyl, aryl, heteroaryl, C 3 -C 24 cycloalkyl, or C 3 -C 24 heterocycloalkyl; and

each R c , independently, is H, C 1 -C 24 alkyl, aryl, heteroaryl, C 3 -C 24 cycloalkyl, or C 3 -C 24 heterocycloalkyl.

6. The article of claim 5 , wherein the second monomer repeat unit comprises a moiety of formula (2), a moiety of formula (6), or a moiety of formula (8).

7. The article of claim 6 , wherein the second monomer repeat unit comprises a moiety of formula (2), in which each X is S, each Y is C(R a ), and each of R 1 and R 2 , independently, is OR c or COOR C .

8. The article of claim 7 , wherein each R a is H and each R c , independently, is C 1 -C 24 alkyl.

9. The article of claim 6 , wherein the second monomer repeat unit comprises a moiety of formula (6), in which each Y is C(R a ) and Z 1 is Si(R a R b ).

10. The article of claim 9 , wherein each R a , independently, is H or C 1 -C 24 alkyl, and R b is C 1 -C 24 alkyl.

11. The article of claim 6 , wherein the second monomer repeat unit comprises a moiety of formula (8), in which Y is C(R a ) and Z 2 is S.

12. The article of claim 11 , wherein R 1 is C 1 -C 24 alkyl and R a is C 1 -C 24 alkyl.

13. The article of claim 6 , wherein the polymer further comprises a third monomer repeat unit different from the first and second monomer repeat units.

14. The article of claim 13 , wherein the third monomer repeat unit comprises a moiety of formula (8):

in which Y is N or C(R a ); Z 2 is O, S, Se, N(R a ), Si(R a R b ), or C(R a R b ); R 1 is H, halo, C 1 -C 24 alkyl, C 2 -C 24 alkenyl, C 2 -C 24 alkynyl, C 3 -C 24 cycloalkyl, C 3 -C 24 cycloalkenyl, C 3 -C 24 heterocycloalkyl, C 3 -C 24 heterocycloalkenyl, aryl, heteroaryl, OR c COR c or COOR c ; each R a , independently, is H, halo, C 1 -C 24 alkyl, aryl, heteroaryl, C 3 -C 24 cycloalkyl, or C 3 -C 24 heterocycloalkyl; R b is H, halo, C 1 -C 24 alkyl, aryl, heteroaryl, C 3 -C 24 cycloalkyl, or C 3 - C 24 heterocycloalkyl; and R 1 is H, C 1 -C 24 alkyl, aryl, heteroaryl, C 3 -C 24 cycloalkyl, or C 3 -C 24 heterocycloalkyl.

15. The article of claim 14 , wherein the third monomer repeat unit comprises a moiety of formula (8), in which Y is C(R a ) and Z 2 is S.

16. The article of claim 15 , wherein, in the moiety of formula (8) in the third monomer repeat unit, R 1 is H and R a is H.

17. The article of claim 16 , wherein the polymer is one of polymers 1-4.

18. The article of claim 13 , wherein the polymer further comprises a fourth monomer repeat unit different from the first, second, and third monomer repeat units.

19. The article of claim 18 , wherein the fourth monomer repeat unit comprises a moiety of formula (13):

in which each Y, independently, is N or C(R a ), each R a , independently, being H, halo, C 1 -C 24 alkyl, aryl, heteroaryl, C 3 -C 24 cycloalkyl, or C 3 -C 24 heterocycloalkyl.

20. The article of claim 19 , wherein the fourth monomer repeat unit comprises a moiety of formula (13), in which each Y is C(R a ).

21. The article of claim 20 , wherein, in the moiety of formula (13) in the fourth monomer repeat unit, each R a is F.

22. The article of claim 21 , wherein the polymer is polymer 5 or polymer 6.

23. A polymer, comprising:

a first monomer repeat unit comprising a moiety of formula (1):

wherein

A is S; and

R is H, C 1 -C 24 alkyl optionally containing oxygen, C 2 -C 24 alkenyl, C 2 -C 24 alkynyl, C 3 -C 24 cycloalkyl, C 3 -C 24 cycloalkenyl, C 3 -C 24 heterocycloalkyl, C 3 -C 24 heterocycloalkenyl, aryl, or heteroaryl.

24. The polymer of claim 23 , wherein R is C 1 -C 24 alkyl optionally containing oxygen and optionally substituted with halo or C 1 -C 24 alkoxy.

25. The polymer of claim 24 , wherein R is C 8 H 17 , C 12 H 25 , or C 20 H 41 .

26. The polymer of claim 22 , wherein the polymer further comprises a second monomer repeat unit different from the first monomer repeat unit.

27. The polymer of claim 26 , wherein the second monomer repeat unit comprises a moiety selected from the group consisting of the moieties of formulas (2)-(23):

wherein

each X, independently, is O, S, or Se;

each Y, independently, is N or C(R a );

Z 1 is N(R a ), S, Si(R a R b ), or C(R a R b );

Z 2 is O, S, Se, N(R a ), Si(R a R b ), or C(R a R b );

Z 3 is O, S, or N(R a );

each Z 4 , independently, is CH 2 , O, or S;

each of R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 , independently, is H, halo, C 1 -C 24 alkyl, C 2 -C 24 alkenyl, C 2 -C 24 alkynyl, C 3 -C 24 cycloalkyl, C 3 -C 24 cycloalkenyl, C 3 -C 24 heterocycloalkyl, C 3 -C 24 heterocycloalkenyl, aryl, heteroaryl, OR c , COR c , or COOR c ;

R 7 is H, C 1 -C 24 alkyl, C 2 -C 24 alkenyl, C 2 -C 24 alkyllyl, C 3 -C 24 cycloalkyl, C 3 -C 24 cycloalkenyl, C 3 -C 24 heterocycloalkyl, C 3 -C 24 heterocycloalkenyl, aryl, heteroaryl, COR c , or COOR c ;

each R a , independently, is H, halo, C 1 -C 24 alkyl, aryl, heteroaryl, C 3 -C 24 cycloalkyl, or C 3 -C 24 heterocycloalkyl;

each R b , independently, is H, halo, C 1 -C 24 alkyl, aryl, heteroaryl, C 3 -C 24 cycloalkyl, or C 3 -C 24 heterocycloalkyl; and

each R c , independently, is H, C 1 -C 24 alkyl, aryl, heteroaryl, C 3 -C 24 cycloalkyl, or C 3 -C 24 heterocycloalkyl.

28. The polymer of claim 27 , wherein the second monomer repeat unit comprises a moiety of formula (2), a moiety of formula (6), or a moiety of formula (8).

29. The polymer of claim 2 , wherein the second monomer repeat unit comprises a moiety of formula (2), in which each X is S, each Y is C(R a ), and each of R 1 and R 2 , independently, is OR c or COOR c .

30. The polymer of claim 29 , wherein each R a is H and each R c , independently, is C 1 -C 24 alkyl.

31. The polymer of claim 28 , wherein the second monomer repeat unit comprises a moiety of formula (6), in which each Y is C(R a ) and Z 1 is Si(R a R b ).

32. The polymer of claim 31 , wherein each R a , independently, is H or C 1 -C 24 alkyl, and R b is C 1 -C 24 alkyl.

33. The polymer of claim 28 , wherein the second monomer repeat unit comprises a moiety of formula (8), in which Y is C(R a ) and Z 2 is S.

34. The polymer of claim 33 , wherein R 1 is C 1 -C 24 alkyl and R a is C 1 -C 24 alkyl.

35. The polymer of claim 28 , wherein the polymer further comprises a third monomer repeat unit different from the first and second monomer repeat units.

36. The polymer of claim 35 , wherein the third monomer repeat unit comprises a moiety of formula (8):

in which Y is N or C(R a ); Z 2 is O, S, Se, N(R a ), Si(R a R b ), or C(R a R b ); R 1 is H, halo, C 1 -C 24 alkyl, C 2 -C 24 alkenyl, C 2 -C 24 alkynyl, C 3 -C 24 cycloalkyl, C 3 -C 24 cycloalkenyl, C 3 -C 24 heterocycloalkyl, C 3 -C 24 heterocycloalkenyl, aryl, heteroaryl, OR c , COR c , or COOR c ; each R a , independently, is H, halo, C 1 -C 24 alkyl, aryl, heteroaryl, C 3 -C 24 cycloalkyl, or C 3 -C 24 heterocycloalkyl; R b is H, halo, C 1 -C 24 alkyl, aryl, heteroaryl, C 3 -C 24 cycloalkyl, or C 3 -C 24 heterocycloalkyl; and R c is H, C 1 -C 24 alkyl, aryl, heteroaryl, C 3 -C 24 cycloalkyl, or C 3 -C 24 heterocycloalkyl.

37. The polymer of claim 36 , wherein the third monomer repeat unit comprises a moiety of formula (8), in which Y is C(R a ) and Z 2 is S.

38. The polymer of claim 37 , wherein, in the moiety of formula (8) in the third monomer repeat unit, R 1 is H and R a is H.

39. The polymer of claim 38 , wherein the polymer is one of polymers 1-4.

40. The polymer of claim 35 , wherein the polymer further comprises a fourth monomer repeat unit different from the first, second, and third monomer repeat units.

41. The polymer of claim 40 , wherein the fourth monomer repeat unit comprises a moiety of formula (13):

in which each Y, independently, is N or C(R a ), each R a , independently, being H, halo, C 1 -C 24 alkyl, aryl, heteroaryl, C 3 -C 24 cycloalkyl, or C 3 -C 24 heterocycloalkyl.

42. The polymer of claim 41 , wherein the fourth monomer repeat unit comprises a moiety of formula (13), in which each Y is C(R a ).

43. The polymer of claim 42 , wherein, in the moiety of formula (13) in the fourth monomer repeat unit, each R a is F.

44. The polymer of claim 43 , wherein the polymer is polymer 5 or polymer 6.