Silole-based polymers and semiconductor materials prepared from the same

1. A polymer comprising a repeating unit of Formula II:

wherein:

Z is S or CR 8 =CR 9 ;

R 1 and R 2 independently are a) H, b) a C 1-20 alkyl group, c) a C 2-20 alkenyl group, d) a C 2-20 alkynyl group, e) a C 1-20 haloalkyl group, f) a —Y—C 3-14 cycloalkyl group, g) a —Y—C 6-14 aryl group, h) a —Y-3-14 membered cycloheteroalkyl group, or i) a —Y-5-14 membered heteroaryl group, wherein each of the C 1-20 alkyl group, the C 2-20 alkenyl group, the C 2-20 alkynyl group, the C 1-20 haloalkyl group, the C 3-14 cycloalkyl group, the C 6-14 aryl group, the 3-14 membered cycloheteroalkyl group, and the 5-14 membered heteroaryl group optionally is substituted with 1-4-Y—R 10 groups;

R 3 , R 4 , R 5 , and R 6 independently are a) H, b) halogen, c) —CN, d) —NO 2 , e) —OH, f) —NH 2 , g) —SH, h) —C(O)OH, i) —C(O)NH 2 , j) —S(O) 2 OH, k) —OC 1-20 alkyl, l) —NH—C 1-20 alkyl, m) —N(C 1-20 alkyl) 2 , n) —C(O)—C 1-20 alkyl, o) —C(O)—OC 1-20 alkyl, p) —C(O)NH—C 1-20 alkyl, q) —C(O)N(C 1-20 alkyl) 2 , r) —S(O) m —C 1-20 alkyl, s) —S(O) m —OC 1-20 alkyl, t) —S(O) m —NHC 1-20 alkyl, u) —S(O) m —N(C 1-20 alkyl) 2 , v) a C 1-20 alkyl group, w) a C 2-20 alkenyl group, x) a C 2-20 alkynyl group, y) a C 1-20 haloalkyl group, z) a C 3-14 cycloalkyl group, aa) a C 6-14 aryl group, ab) a 3-14 membered cycloheteroalkyl group, or ac) a 5-14 membered heteroaryl group; wherein each of the C 1-20 alkyl groups, the C 2-20 alkenyl group, the C 2-20 alkynyl group, the C 1-20 haloalkyl group, the C 3-14 cycloalkyl group, the C 6-14 aryl group, the 3-14 membered cycloheteroalkyl group, and the 5-14 membered heteroaryl group optionally is substituted with 1-4-Y—R 10 groups;

R 8 and R 9 independently are a) H, b) halogen, c) —CN, d) —NO 2 , e) —OH, f) —NH 2 , g) —SH, h) —C(O)OH, i) —C(O)NH 2 , j) —S(O) 2 OH, k) —OC 1-20 alkyl, l) —NH—C 1-20 alkyl, m) —N(C 1-20 alkyl) 2 , n) —C(O)—C 1-20 alkyl, o) —C(O)—OC 1-20 alkyl, p) —C(O)NH—C 1-20 alkyl, q) —C(O)N(C 1-20 alkyl) 2 , r) —S(O) m —C 1-20 alkyl, s) —S(O) m —OC 1-20 alkyl, t) —S(O) m —NHC 1-20 alkyl, u) —S(O) m —N(C 1-20 alkyl) 2 , v) a C 1-20 alkyl group, w) a C 2-20 alkenyl group, x) a C 2-20 alkynyl group, y) a C 1-20 haloalkyl group, z) a C 3-14 cycloalkyl group, aa) a C 6-14 aryl group, ab) a 3-14 membered cycloheteroalkyl group, or ac) a 5-14 membered heteroaryl group, wherein each of the C 1-20 alkyl groups, the C 2-20 alkenyl group, the C 2-20 alkynyl group, the C 1-20 haloalkyl group, the C 3-14 cycloalkyl group, the C 6-14 aryl group, the 3-14 membered cycloheteroalkyl group, and the 5-14 membered heteroaryl group optionally is substituted with 1-4-Y—R 10 groups;

R 10 , at each occurrence, independently is a) halogen, b) —NO 2 , c) —CN, d) oxo, e) —OH, f) —NH 2 , g) —SH, h) —C(O)OH, i) —C(O)NH 2 , j) —S(O) 2 OH, k) —OC 1-20 alkyl, l) —NH—C 1-20 alkyl, m) —N(C 1-20 alkyl) 2 , n) —C(O)—C 1-20 alkyl, o) —C(O)—OC 1-20 alkyl, p) —C(O)NH—C 1-20 alkyl, q) —C(O)N(C 1-20 alkyl) 2 , r) —S(O) m —C 1-20 alkyl, s) —S(O) m —OC 1-20 alkyl, t) —S(O) m —NHC 1-20 alkyl, u) —S(O) m —N(C 1-20 alkyl) 2 , v) a C 1-20 alkyl group, w) a C 2-20 alkenyl group, x) a C 2-20 alkynyl group, y) a C 1-20 haloalkyl group, z) a C 3-14 cycloalkyl group, aa) a C 6-14 aryl group, ab) a 3-14 membered cycloheteroalkyl group, or ac) a 5-14 membered heteroaryl group;

Y, at each occurrence, independently is a) a divalent C 1-20 alkyl group, b) a divalent C 2-20 alkenyl group, c) a divalent C 2-20 alkynyl group, d) a divalent C 1-20 haloalkyl group, or e) a covalent bond;

m, at each occurrence, independently is 0, 1, or 2; and

x is 2, 3, 4, 5, 6, 7, 8, 9, or 10.

2. The polymer of claim 1 , wherein Z is S.

3. The polymer of claim 1 , wherein Z is CH═CH.

4. The polymer of claim 1 , wherein R 1 and R 2 independently are a C 1-20 alkyl group optionally substituted with 1-4-Y—R 10 groups.

5. The polymer of claim 1 , wherein at least one of R 3 , R 4 , R 5 , and R 6 is H.

6. The polymer of claim 1 , wherein the repeating unit has Formula III:

wherein Z is S or CH═CH; x is 2; and R 1 and R 2 are as defined in claim 1 .

7. The polymer of claim 6 , wherein R 1 and R 2 independently are a hexyl group or an octyl group.

8. The polymer of claim 1 , wherein the polymer has Formula II′ or Formula III′:

wherein n is an integer in the range from 2 to about 500;

X is 2; and

R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and Z are as defined in claim 1 .

9. The polymer of claim 1 , wherein the polymer is

wherein n is an integer in the range from 2 to about 500.

10. The polymer of claim 1 , wherein the polymer comprises one or more additional repeating units other than the repeating unit of Formula II.

11. The polymer of claim 10 , wherein the one or more additional repeating units are selected from:

wherein R 3 , R 4 , R 5 , R 6 , R 8 , and R 9 are as defined in claim 1 .

12. A composition comprising one or more polymers of claim 1 dissolved in an organic solvent or a mixture of solvents.

13. A thin film semiconductor comprising one or more polymers of claim 1 .

14. A composite comprising a substrate and the thin film semiconductor of claim 13 deposited on the substrate.

15. An organic field effect transistor device comprising the composite of claim 14 .

16. A complementary circuit comprising the thin film semiconductor of claim 13 .

17. An electronic device comprising the complementary circuit of claim 16 .

18. A composition comprising one or more polymers of claim 6 dissolved in an organic solvent or a mixture of solvents.

19. A thin film semiconductor comprising one or more polymers of claim 6 .

20. An organic field effect transistor device comprising a substrate and the thin film semiconductor of claim 19 deposited on the substrate.