Bithiophene sulfonamide-based molecular and polymeric semiconductors

1. A semiconducting compound comprising one or more optionally substituted bithiophene sulfonamide moieties, wherein the one or more optionally substituted bithiophene sulfonamide moieties are identical or different, each being represented by formula (I):

wherein:

R 1 is selected from the group consisting of H, 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 1-40 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), —Si(C 1-40 alkyl) 3 , —Si(C 1-40 alkyl) 2 (—O—Si(C 1-40 alkyl) 3 ), —Si(C 1-40 alkyl)(—O—Si(C 1-40 alkyl) 3 ) 2 , —Si(—O—Si(C 1-40 alkyl) 3 ) 3 , —O—SiH 3 , —O—SiH(C 1-40 alkyl) 2 , —O—SiH 2 (C 1-40 alkyl), —O—Si(C 1-40 alkyl) 3 , —O—Si(C 1-40 alkyl) 2 (—O—Si(C 1-40 alkyl) 3 ), and —O—Si(C 1-40 alkyl)(—O—Si(C 1-40 alkyl) 3 ) 2 ; and

R 2 and R 3 independently are selected from the group consisting of H, F, Cl, —CN, a C 1-40 alkyl group, a C 2-40 alkenyl group, a C 2-40 alkynyl group, a C 1-40 haloalkyl group, a C 1-40 alkoxy group, and a C 1-40 thioalkyl group, wherein each of the C 1-40 alkyl group, the C 2-40 alkenyl group, the C 2-40 alkynyl group, the C 1-40 haloalkyl group, the C 1-40 alkoxy group, and the C 1-40 thioalkyl group optionally is substituted with 1-5 substituents independently selected from a halogen, —CN, NO 2 , OH, —NH 2 , —NH(C 1-6 alkyl), —N(C 1-6 alkyl) 2 , —S(O) 2 OH, —CHO, —C(O)—C 1-6 alkyl, —C(O)OH, —C(O)—OC 1-6 alkyl, —C(O)NH 2 , —C(O)NH—C 1-6 alkyl, —C(O)N(C 1-6 alkyl) 2 , —OC 1-6 alkyl, —SiH 3 , —SiH(C 1-40 alkyl) 2 , —SiH 2 (C 1-40 alkyl), —Si(C 1-40 alkyl) 3 , —Si(C 1-40 alkyl) 2 (—O—Si(C 1-40 alkyl) 3 ), —Si(C 1-40 alkyl)(-O—Si(C 1-40 alkyl) 3 ) 2 , —Si(—O—Si(C 1-40 alkyl) 3 ) 3 , —O—SiH 3 , alkyl) 2 , —O—SiH 2 (C 1-40 alkyl), —O—Si(C 1-40 alkyl) 3 alkyl) 3 ), and —O—Si(C 1-40 alkyl)(-O—Si(C 1-40 alkyl) 3 ) 2 .

2. The compound of claim 1 , wherein R 1 is selected from the group consisting of:

a) a linear C 6-40 alkyl, alkenyl, alkynyl or halolalkyl group optionally 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), —Si(C 1-40 alkyl) 3 , —Si(C 1-40 alkyl) 2 (—O—Si(C 1-40 alkyl) 3 ), —Si(C 1-40 alkyl)(-O—Si(C 1-40 alkyl) 3 ) 2 , —Si(—O—Si(C 1-40 alkyl) 3 ) 3 , —O—SiH 3 , —O—SiH(C 1-40 alkyl) 2 , —O—SiH 2 (C 1-40 alkyl), —O—Si(C 1-40 alkyl) 3 , —O—Si(C 1-40 alkyl) 2 (—O—Si(C 1-40 alkyl) 3 ), and —O—Si(C 1-40 alkyl)(-O—Si(C 1-40 alkyl) 3 ) 2 ;

b) a branched C 6-40 alkyl, alkenyl, alkynl or halolalkyl group having the formula —CHR′ 2 , where each R′ independently is a C 1-20 alkyl group, a C 1-20 haloalkyl group, a C 2-20 alkenyl group, or a C 2-20 alkynyl group, each of which optionally is substituted with 1-10 substituents independently selected from a halogen, —CN, NO 2 , OH, —NH 2 , —NH(C 1-40 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), —Si(C 1-40 alkyl) 3 , —Si(C 1-40 alkyl) 2 (—O—Si(C 1-40 alkyl) 3 ), —Si(C 1-40 alkyl)(-O—Si(C 1-40 alkyl) 3 ) 2 , —Si(—O—Si(C 1-40 alkyl) 3 ) 3 , —O—SiH 3 , —O—SiH(C 1-40 alkyl) 2 , —O—SiH 2 (C 1-40 alkyl), —O—Si(C 1-40 alkyl) 3 , —O—Si(C 1-40 alkyl) 2 (—O—Si(C 1-40 alkyl) 3 ), and —O—Si(C 1-40 alkyl)(-O—Si(C 1-40 alkyl) 3 ) 2 ; and

c) a branched C 6-40 alkyl, alkenyl, alkynl or halolalkyl group having the formula —CH 2 —CHR′ 2 , where each R′ independently is a C 1-20 alkyl group, a C 1-20 haloalkyl group, a C 2-20 alkenyl group, or a C 2-20 alkynyl group, each of which optionally is substituted with 1-10 substituents independently selected from a halogen, —CN, NO 2 , OH, —NH 2 , —NH(C 1-40 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), —Si(C 1-40 alkyl) 3 , —Si(C 1-40 alkyl) 2 (—O—Si(C 1-40 alkyl) 3 ), —Si(C 1-40 alkyl)(-O—Si(C 1-40 alkyl) 3 ) 2 , —Si(—O—Si(C 1-40 alkyl) 3 ) 3 , —O—SiH 3 , —O—SiH(C 1-40 alkyl) 2 , —O—SiH 2 (C 1-40 alkyl), —O—Si(C 1-40 alkyl) 3 , —O—Si(C 1-40 alkyl) 2 (—O—Si(C 1-40 alkyl) 3 ), and —O—Si(C 1-40 alkyl)(-O—Si(C 1-40 alkyl) 3 ) 2 .

3. The compound of claim 2 , wherein R 2 and R 3 are H.

4. The compound of claim 1 , wherein the compound is a polymer having a first repeating unit M 1 comprising one or more optionally substituted bithiophene sulfonamide moieties represented by formula (I) and wherein said polymer has a degree of polymerization (n) ranging from 3 to 1,000.

5. The compound of claim 4 , wherein M 1 has a formula selected from the group consisting of:

wherein:

pi-2 is an optionally substituted conjugated polycyclic moiety other than an optionally substituted bithiophene sulfonamide moiety;

Ar, at each occurrence, is independently an optionally substituted 5- or 6-membered aryl or heteroaryl group;

Z is a conjugated noncyclic linker;

m and m′ independently are 0, 1, 2, 3, 4, 5 or 6, provided that at least one of m and m′ is not 0;

m″ is 1, 2, 3, 4, 5 or 6; and

p and p′ independently are 0 and 1, provided that at least one of p and p′ is 1.

6. The compound of claim 5 , wherein pi-2 is an optionally substituted C 8-26 aryl group or 8-26 membered heteroaryl group.

7. The compound of claim 6 , wherein pi-2 is selected from the group consisting of:

wherein:

R a is selected from the group consisting of H, F, Cl, —CN, R, —OR, —SR, —C(O)R, —OC(O)R, and —C(O)OR;

R b is selected from the group consisting of H, R, and -L-R f ;

R c is H or R;

R d is selected from the group consisting of H, F, Cl, —CN, R, —OR, —SR, —C(O)R, —OC(O)R, —C(O)OR, and -L-R f ;

R e is selected from the group consisting of H, F, Cl, —CN, R, —OR, —SR, —C(O)R, —OC(O)R, —C(O)OR, and R f ;

R f is a C 6-20 aryl group or a 5-20-membered heteroaryl group, each optionally substituted with 1-8 groups independently selected from the group consisting of F, Cl, —CN, R, —OR, and —SR;

L is selected from the group consisting of —O—, —S—, —C(O)—, —OC(O)—, —C(O)O—, and a covalent bond; and

R is selected from the group consisting of a C 1-40 alkyl group, a C 1-40 haloalkyl group, a C 2-40 alkenyl group, and a C 2-40 alkynyl group.

8. The compound of claim 5 , wherein Ar in (Ar) m , (Ar) m′ , and (Ar) m″ is represented by:

wherein each W independently is selected from N, CH, and CR 4 , wherein R 4 is selected from F, Cl, —CN, R, OR, SR, C(O)R, OC(O)R, and C(O)OR, and wherein R 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.

9. The compound of claim 8 , wherein (Ar) m , (Ar) m′ , and (Ar) m″ independently are selected from:

10. The compound of claim 5 , wherein Z is selected from:

wherein R 4 is selected from F, Cl, —CN, R, OR, SR, C(O)R, OC(O)R, and C(O)OR, and wherein R 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.

11. The compound of claim 4 , further comprising one or more repeating units other than M 1 , the one or more other repeating units (M 2 ) being selected from:

wherein:

pi-2 is an optionally substituted conjugated polycyclic moiety other than an optionally substituted bithiophene sulfonamide moiety;

Ar, at each occurrence, is independently an optionally substituted 5- or 6-membered aryl or heteroaryl group;

Z is a conjugated noncyclic linker;

m and m′ independently are 0, 1, 2, 3, 4, 5 or 6, provided that at least one of m and m′ is not 0;

m″ is 1, 2, 3, 4, 5 or 6; and

p and p′ independently are 0 and 1, provided that at least one of p and p′ is 1.

12. The compound of claim 11 , wherein:

Z is selected from the group consisting of:

(Ar) m (Ar) m′ , and (Ar) m″ independently are selected from the group consisting of:

wherein R 4 is selected from F, Cl, —CN, R, OR, SR, C(O)R, OC(O)R, and C(O)OR, and wherein R 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; and

pi-2 is selected from the group consisting of:

wherein:

R a is selected from the group consisting of H, F, Cl, —CN, R, —OR, —SR, —C(O)R, —OC(O)R, and —C(O)OR;

R b is selected from the group consisting of H, R, and -L-R f ;

R c is H or R;

R d is selected from the group consisting of H, F, Cl, —CN, R, —OR, —SR, —C(O)R, —OC(O)R, —C(O)OR, and -L-R f ; and

R e is selected from the group consisting of H, F, Cl, —CN, R, —OR, —SR, —C(O)R, —OC(O)R, —C(O)OR, and R f ; wherein

R f is a C 6-20 aryl group or a 5-20-membered heteroaryl group, each optionally substituted with 1-8 groups independently selected from the group consisting of F, Cl, —CN, R, —OR, and —SR;

L is selected from the group consisting of —O—, —S—, —C(O)—, —OC(O)—, —C(O)O—, and a covalent bond; and R is selected from the group consisting of a C 1-40 alkyl group, a C 1-40 haloalkyl group, a C 2-40 alkenyl group, and a C 2-40 alkynyl group; and

R is selected from the group consisting of a C 1-40 alkyl group, a C 1-40 haloalkyl group, a C 2-40 alkenyl group, and a C 2-40 alkynyl group.

13. The compound of claim 12 , wherein M 1 is selected from the group consisting of:

M 2 is selected from the group consisting of:

wherein (Ar) m and (Ar) m′ are selected from:

and R 4 is selected from the group consisting of F, Cl, —CN, R, OR, SR, C(O)R, OC(O)R, and C(O)OR; wherein R is selected from the group consisting of 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.

14. The compound of claim 11 , wherein the compound is a copolymer having a formula selected from the group consisting of:

wherein M 1A and M 1B represent different repeating units having the formula M 1 , and M 2A and M 2B represent different repeating units having the formula M 2 , x and y are real numbers representing molar ratios, and n is the degree of polymerization.

15. The compound of claim 1 , wherein the compound has a formula selected from the group consisting of:

wherein:

Q 1 and Q 2 independently are selected from the group consisting of H, R, and C(O)R, wherein R is a C 1-40 alkyl or haloalkyl group;

pi-2 is an optionally substituted conjugated polycyclic moiety other than an optionally substituted bithiophene sulfonamide moiety;

Ar, at each occurrence, is independently an optionally substituted 5- or 6-membered aryl or heteroaryl group;

Z is a conjugated noncyclic linker;

m and m′ independently are 0, 1, 2, 3, 4, 5 or 6, provided that at least one of m and m′ is not 0;

m″ is 1, 2, 3, 4, 5 or 6; and

p and p′ independently are 0 and 1, provided that at least one of p and p′ is 1.

16. The compound of claim 15 , wherein the compound is represented by a formula selected from the group consisting of:

wherein R 5 is H or R.