Polymeric semiconductors and related devices

1. A polymeric compound comprising in its backbone 4 to 10,000 identical or different bithiophene-3,3′dicarboximide-2,2′-diyl groups.

2. A polymeric compound comprising in its backbone 4 to 10,000 identical or different repeating units of the formula:

wherein:

X is selected from O, S, and Se; and

R 1 is selected from H, a C 1-40 alkyl group, a C 2-40 alkenyl group, a C 1-40 haloalkyl group, and an organic group comprising 1-4 cyclic moieties,

wherein:

each of the C 1-40 alkyl group, the C 2-40 alkenyl group, and the C 1-40 haloalkyl group optionally is substituted with 1-10 substituents independently selected from a halogen, —CN, NO 2 , OH, —NH 2 , —NH(C 1-40 alkyl), —N(C 1-40 alkyl) 2 , —S(O) 2 OH, —CHO, —C(O)—C 1-40 alkyl, —C(O)OH, —C(O)—OC 1-40 alkyl, —C(O)NH 2 , —C(O)NH—C 1-40 alkyl, —C(O)N(C 1-40 alkyl) 2 , —OC 1-40 alkyl, —SiH 3 , —SiH(C 1-40 alkyl) 2 , —SiH 2 (C 1-40 alkyl), and —Si(C 1-40 alkyl) 3 ;

each of the C 1-40 alkyl group, the C 2-40 alkenyl group, and the C 1-40 haloalkyl group is bonded covalently either directly to the imide nitrogen atom or via linker; and

each of the 1-4 cyclic moieties of the organic group is the same or different, is bonded covalently to each other or the imide nitrogen via an optional linker, and optionally is substituted with 1-5 substituents independently selected from a halogen, oxo, —CN, NO 2 , OH, ═C(CN) 2 , —NH 2 , —NH(C 1-40 alkyl), —N(C 1-40 alkyl) 2 , —S(O) 2 OH, —CHO, —C(O)OH, —C(O)—C 1-40 alkyl, —C(O)—OC 1-40 alkyl, —C(O)NH 2 , —C(O)NH—C 1-40 alkyl, —C(O)N(C 1-40 alkyl) 2 , —SiH 3 , —SiH(C 1-40 alkyl) 2 , —SiH 2 (C 1-40 alkyl), —Si(C 1-40 alkyl) 3 , —O—C 1-40 alkyl, —O—C 1-40 alkenyl, —O—C 1-40 haloalkyl, a C 1-40 alkyl group, a C 1-40 alkenyl group, and a C 1-40 haloalkyl group.

3. The polymeric compound of claim 2 comprising at least one other repeating unit, wherein the other repeating unit comprises:

an electron-rich conjugated system selected from:

wherein each group optionally is substituted with 1-6 electron-donating groups;

an electron-poor conjugated system selected from:

and a polycyclic group comprising 1-6 electron-withdrawing groups; or

an electron-neutral conjugated system selected from:

wherein:

T is selected from O, S, and NR 2 ;

T 1 and T 2 independently are selected from N and CR 3 , provided that at least one of T 1 and T 2 is N;

T 3 and T 4 independently are selected from N and CR 4 , provided that at least one of T 3 and T 4 is N;

R 2 is H or an electron-donating group;

R 3 , at each occurrence, independently is an electron-withdrawing group;

R 4 , at each occurrence, independently is H or an electron-donating group; and

m is 1, 2, 3, 4, 5 or 6.

4. The polymeric compound of claim 2 having the formula:

wherein R 1 is a C 1-20 alkyl group and n is an integer between 4 and 5,000.

5. The polymeric compound of claim 2 having the formula:

wherein R 1 is a C 1-20 alkyl group and n is an integer between 4 and 5,000.

6. The polymeric compound of claim 2 having the formula:

wherein:

M 2 is

R 4 , at each occurrence, independently is selected from H, a C 1-10 alkyl group, and a C 1-10 alkoxyl group, provided that at least one R 4 is not H;

m is 1, 2, 3, 4, 5 or 6;

n is an integer between 4 and 5,000; and

R 1 and X are as defined in claim 2 .

7. The polymeric compound of claim 2 having the formula:

wherein:

M 2 is

R 5 , at each occurrence, independently is a C 1-10 alkyl group;

n is an integer between 4 and 5,000; and

R 1 and X are as defined in claim 2 .

8. The polymeric compound of claim 2 having the formula:

wherein:

M 2 is

R 2 is H or a C 1-10 alkyl group;

R 4 , at each occurrence, independently is selected from H, a C 1-10 alkyl group, and a C 1-10 alkoxyl group;

m is 1, 2, 3, 4, 5 or 6;

n is an integer between 4 and 5,000; and

R 1 and X are as defined in claim 2 .

9. The polymeric compound of claim 2 having the formula:

wherein:

M 2 is

wherein either group optionally is substituted with 1-6 groups independently selected from a C 1-10 alkyl group and a C 1-10 alkoxyl group;

R 2 is H or a C 1-10 alkyl group;

n is an integer between 4 and 5,000; and

R 1 and X are as defined in claim 2 .

10. The polymeric compound of claim 2 having the formula:

wherein:

M 2 is selected from:

wherein:

R 3 , at each occurrence, independently is selected from F and CN;

m is 1, 2, 3, 4, 5 or 6;

m′ is 1, 2 or 3;

n is an integer between 4 and 5,000; and

R 1 and X are as defined in claim 2 .

11. The polymeric compound of claim 2 having the formula:

wherein:

M 2 is a polycyclic group comprising 1-6 electron-withdrawing groups independently selected from oxo, F, CN, and ═C(CN) 2 ;

n is an integer between 4 and 5,000; and

R 1 and X are as defined in claim 2 .

12. The polymeric compound of claim 2 having the formula:

wherein:

M 2 is selected from:

wherein:

R 3 , at each occurrence, independently is selected from F and CN;

R 6 is a C 1-20 alkyl group;

n is an integer between 4 and 5,000; and

R 1 and X are as defined in claim 2 .

13. The polymeric compound of claim 2 having the formula:

wherein:

M 2 is selected from:

R 5 , at each occurrence, independently is a C 1-10 alkyl group;

m′ is 1, 2 or 3;

n is an integer between 4 and 5,000; and

R 1 and X are as defined in claim 2 .

14. The polymeric compound of claim 2 , wherein X is O.

15. The polymeric compound of claim 2 , wherein R 1 is selected from H, -L-R a , -L′-Cy 1 , -L′-Cy 1 -L′-Cy 2 , -L′-Cy 1 -L′-Cy 2 -Cy 2 , -L′-Cy 1 -Cy 1 , -L′-Cy 1 -Cy 1 -L′-Cy 2 , -L′-Cy 1 -Cy 1 -L′-Cy 2 -Cy 2 , -L′-Cy 1 -L-R a , -L′-Cy 1 -L′-Cy 2 -L-R a , -L′-Cy 1 -L′-Cy 2 -Cy 2 -L-R a , -L′-cy 1 -Cy 1 -L-R a , and -L′-Cy 1 -Cy 1 -L′-Cy 2 -L-R a ;

wherein:

Cy 1 and Cy 2 independently are selected from a C 6-14 aryl group, a 5-14 membered heteroaryl group, a C 3-14 cycloalkyl group, and a 3-14 membered cycloheteroalkyl group, each of which optionally is substituted with 1-5 substituents independently selected from a halogen, —CN, oxo, ═C(CN) 2 , a C 1-6 alkyl group, a C 1-6 alkoxy group, and a C 1-6 haloalkyl group;

L, at each occurrence, independently is a covalent bond or a linker selected from —Y—O—Y—, —Y—[S(O) w ]—Y—, —Y—C(O)—Y—, —Y—[NR c C(O)]—Y—, —Y—[C(O)NR c ]—, —Y—NR c —, —Y—[SiR c 2 ]—Y—, a divalent C 1-40 alkyl group, a divalent C 2-40 alkenyl group, and a divalent C 1-40 haloalkyl group;

L′, at each occurrence, independently is a covalent bond or a linker selected from —Y—O—Y—, —Y—[S(O) w ]—Y—, —Y—C(O)—Y—, —Y—[NR c C(O)]—Y—, —Y—[C(O)NR c ]—, —Y—NR c —, —Y—[SiR c 2 ]—Y—, a divalent C 1-40 alkyl group, a divalent C 2-40 alkenyl group, and a divalent C 1-40 haloalkyl group;

wherein:

Y, at each occurrence, independently is selected from a divalent C 1-40 alkyl group, a divalent C 2-40 alkenyl group, a divalent C 1-40 haloalkyl group, and a covalent bond;

R c is selected from H, a C 1-6 alkyl group, a C 6-14 aryl group, and a —C 1-6 alkyl-C 6-14 aryl group; and

w is 0, 1, or 2; and

R a is selected from a C 1-40 alkyl group, a C 2-40 alkenyl group, a C 2-40 alkynyl group, and a C 1-40 haloalkyl group, each of which optionally is substituted with 1-10 substituents independently selected from a halogen, —CN, NO 2 , OH, —NH 2 , —NH(C 1-20 alkyl), —N(C 1-20 alkyl) 2 , —S(O) 2 OH, —CHO, —C(O)—C 1-20 alkyl, —C(O)OH, —C(O)—OC 1-20 alkyl, —C(O)NH 2 , —C(O)NH—C 1-20 alkyl, —C(O)N(C 1-20 alkyl) 2 , —OC 1-20 alkyl, —SiH 3 , —SiH(C 1-20 alkyl) 2 , —SiH 2 (C 1-20 alkyl), and —Si(C 1-20 alkyl) 3 .

16. The polymeric compound of claim 2 , wherein R 1 is selected from:

17. The polymeric compound of claim 2 , wherein R 1 is a linear or branched C 3-40 alkyl or C 3-40 alkenyl group.

18. The polymeric compound of claim 2 , wherein R 1 is selected from:

19. The polymeric compound of 2 having the formula:

wherein:

Ar, at each occurrence, independently comprises 1-6 optionally substituted monocyclic aryl or heteroaryl moieties;

X is O, S, or Se;

Z is a linear or cyclic linker;

R 1 is selected from H, -L-R a , -L′-Cy 1 , -L′-Cy 1 -L′-Cy 2 , -L′-Cy 1 -L′-Cy 2 -Cy 2 , -L′-Cy 1 -Cy 1 , -L′-Cy 1 -Cy 1 -L′-Cy 2 , -L′-Cy 1 -Cy 1 -L′-Cy 2 -Cy 2 , -L′-Cy 1 -L-R a , -L′-Cy 1 -L′-Cy 2 -L-R a , -L′-Cy 1 -L′-Cy 2 -Cy 2 -L-R a , -L′-cy 1 -Cy 1 -L-R a , and -L′-Cy 1 -Cy 1 -L′-Cy 2 -L-R a ;

wherein:

Cy 1 and Cy 2 independently are selected from a C 6-14 aryl group, a 5-14 membered heteroaryl group, a C 3-14 cycloalkyl group, and a 3-14 membered cycloheteroalkyl group, each of which optionally is substituted with 1-5 substituents independently selected from a halogen, —CN, oxo, ═C(CN) 2 , a C 1-6 alkyl group, a C 1-6 alkoxy group, and a C 1-6 haloalkyl group;

L, at each occurrence, independently is a covalent bond or a linker selected from —Y—O—Y—, —Y—[S(O) w ]—Y—, —Y—C(O)—Y—, —Y—[NR c C(O)]—Y—, —Y—[C(O)NR c ]—, —Y—NR c —, —Y—[SiR c 2 ]—Y—, a divalent C 1-40 alkyl group, a divalent C 2-40 alkenyl group, and a divalent C 1-40 haloalkyl group;

L′, at each occurrence, independently is a covalent bond or a linker selected from —Y—O—Y—, —Y—[S(O) w ]—Y—, —Y—C(O)—Y—, —Y—[NR c C(O)]—Y—, —Y—[C(O)NR c ]—, —Y—NR c —, —Y—[SiR c 2 ]—Y—, a divalent C 1-40 alkyl group, a divalent C 2-40 alkenyl group, and a divalent C 1-40 haloalkyl group;

wherein:

Y, at each occurrence, independently is selected from a divalent C 1-40 alkyl group, a divalent C 2-40 alkenyl group, a divalent C 1-40 haloalkyl group, and a covalent bond;

R c is selected from H, a C 1-6 alkyl group, a C 6-14 aryl group, and a —C 1-6 alkyl-C 6-14 aryl group; and

w is 0, 1, or 2; and

R a is selected from a C 1-40 alkyl group, a C 2-40 alkenyl group, a C 2-40 alkynyl group, and a C 1-40 haloalkyl group, each of which optionally is substituted with 1-10 substituents independently selected from a halogen, —CN, NO 2 , OH, —NH 2 , —NH(C 1-20 alkyl), —N(C 1-20 alkyl) 2 , —S(O) 2 OH, —CHO, —C(O)—C 1-20 alkyl, —C(O)OH, —C(O)—OC 1-20 alkyl, —C(O)NH 2 , —C(O)NH—C 1-20 alkyl, —C(O)N(C 1-20 alkyl) 2 , —OC 1-20 alkyl, —SiH 3 , —SiH(C 1-20 alkyl) 2 , —SiH 2 (C 1-20 alkyl), and —Si(C 1-20 alkyl) 3 ; and

n is an integer greater than 2.

20. An electronic, opto-electronic, or optical device comprising a semiconductor material, the semiconductor material comprising one or more polymeric compounds of claim 2 , wherein the electronic, opto-electronic, or optical device optionally is selected from a field effect transistor, an organic light-emitting transistor, and an organic photovoltaic device.

21. The polymeric compound of claim 19 having a formula selected from:

wherein:

R 9 , at each occurrence, independently is selected from H, halogen, a C 1-10 alkyl group, a C 1-10 alkoxy group, and a C 1-10 haloalkyl group; and

R 1 and n are as defined in claim 19 .