IP Library › Granted Patent US 7,816,480

Granted Patent B2

US 7,816,480 · App. 12/563,680 · Granted Oct 19, 2010

Silole-based polymers and semiconductor materials prepared from the same

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Quick Facts

Patent No.: US 7,816,480
App. No.: 12/563,680
Granted: Oct 19, 2010
Kind: B2

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Abstract

The present teachings provide silole-based polymers that can be used as p-type semiconductors. More specifically, the present teachings provide polymers that include a repeating unit of Formula I: wherein R 1 , R 2 , R 3 , R 4 , R 5 R 6 , Z, x, and x′ are as defined herein. The present teachings also provide methods of preparing these polymers, and relate to various compositions, composites, and devices that incorporate these polymers.

Claims (58)

1. A polymer comprising a first repeating unit of the formula:

and a second repeating unit comprising one or more optionally substituted 5-14 membered heteroaryl groups, one or more optionally substituted C 6-14 aryl groups, or combinations thereof,

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, provided that at least one of R 5 and R 6 is not H;

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, 1) —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; and

m, at each occurrence, independently is 0, 1, or 2.

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

3. 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.

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

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

6. The polymer of claim 1 , wherein the second repeating unit comprises one or more optionally substituted polycyclic 8-14 membered heteroaryl groups.

7. The polymer of claim 1 , wherein the second repeating unit comprises an optionally substituted polycyclic heteroaryl group, wherein the optionally substituted polycyclic heteroaryl group comprises an optionally substituted thienyl group fused with an optionally substituted 5- or 6-membered heteroaryl group.

8. The polymer of claim 7 , wherein the second repeating unit is:

wherein R 3 and R 4 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;

9. The polymer of claim 1 , wherein the second repeating unit comprises one or more optionally substituted phenyl groups.

10. The polymer of claim 9 , wherein the second repeating unit is selected from:

wherein 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 is 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;

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

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

13. A composite comprising a substrate and the thin film semiconductor of claim 12 deposited on the substrate.

14. An organic field effect transistor device comprising the thin film semiconductor of claim 12 .

15. An organic light-emitting diode comprising the thin film semiconductor of claim 12 .

16. An organic photovoltaic device comprising the thin film semiconductor of claim 12 .

17. A polymer comprising a first repeating unit of the formula:

and a second repeating unit comprising one or more optionally substituted 5-14 membered heteroaryl groups, one or more optionally substituted C 6-14 aryl groups, or combinations thereof,

wherein:

Z is S or CR 8 ═CR 9 ;

R 1 and R 2 independently are a C 1-20 alkyl group optionally 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;

m, at each occurrence, independently is 0, 1, or 2.

18. The polymer of claim 17 , wherein the first repeating unit has the formula:

wherein R 1 , R 2 , and Z are as defined in claim 17 .

19. The polymer of claim 17 , wherein the first repeating unit is selected from:

20. A polymer comprising a first repeating unit of the formula:

and a second repeating unit comprising one or more optionally substituted polycyclic 8-14 membered heteroaryl groups,

wherein:

Z is S or CR 8 ═CR 9 ;

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, 1) —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;

m, at each occurrence, independently is 0, 1, or 2.

21. The polymer of claim 20 , wherein the optionally substituted polycyclic heteroaryl group of the second repeating unit comprises an optionally substituted thienyl group fused with an optionally substituted 5- or 6-membered heteroaryl group.

22. The polymer of claim 20 , wherein the second repeating unit is selected from

wherein R 3 , R 4 , R 5 , R 6 , R 8 , and R 9 are as defined in claim 20 .

Assignments (4)

CONFIRMATORY LICENSE Recorded Jun 25, 2015

From: NORTHWESTERN UNIVERSITY

To: USA AS REPRESENTED BY THE ADMINISTRATOR OF THE NASA

Reel/Frame 035908/0960 →

RELEASE OF SECURITY INTEREST Recorded Jun 5, 2012

From: SOLVAY NORTH AMERICA INVESTMENTS, LLC

To: POLYERA CORPORATION

Reel/Frame 028323/0253 →

SECURITY AGREEMENT Recorded Jul 27, 2011