Polymers of thieno[3,4-b]furan, method of making, and use thereof

1. A polymer, comprising:

units derived from thieno[3,4-b]furan according to the structures (I), (II), or (III):

wherein R a is hydrogen, hydroxyl, C 6 -C 12 aryl, C 3 -C 10 cycloalkyl, C 1 -C 12 alkyl, halogen, C 1 -C 12 alkoxy, C 1 -C 12 alkylthio, C 1 -C 12 haloalkyl, C 1 -C 12 haloalkoxy, C 6 -C 12 haloaryl, pyridyl, cyano, thiocyanato, nitro, amino, C 1 -C 12 alkylamino, C 1 -C 12 aminoalkyl, acyl, sulfoxyl, sulfonyl, sulfonate, phosphonate, amido, or carbamoyl.

2. The polymer of claim 1 , wherein the polymer is a homopolymer.

3. The polymer of claim 2 , wherein R a is hydrogen or C 1 -C 6 alkyl.

4. The polymer of claim 1 , wherein the polymer is a copolymer comprising, in addition to the units derived from thieno[3,4-b]furan, units derived from a co-monomer reactive with the thieno[3,4-b]furan.

5. The polymer of claim 4 , wherein the co-monomer is a substituted thieno[3,4-b]furan, thiophene, substituted thiophene, thieno[3,4-b]thiophene, substituted thienothiophene, dithieno[3,4-b:3′,4′-d]thiophene, bithiophene, pyrrole, substituted pyrrole, phenylene, substituted phenylene, naphthalene, substituted naphthalene, biphenyl, substituted biphenyl, terphenyl, substituted terphenyl, phenylene vinylene, substituted phenylene vinylene, or a combination comprising at least one of the foregoing co-monomers, wherein the substituents are one or more of hydroxyl, C 6 -C 12 aryl, C 3 -C 10 cycloalkyl, C 1 -C 12 alkyl, halogen, C 1 -C 12 alkoxy, C 1 -C 12 alkylthio, C 1 -C 12 haloalkyl, C 6 -C 12 haloaryl, pyridyl, cyano, thiocyanato, nitro, amino, C 1 -C 12 alkylamino, C 1 -C 12 aminoalkyl, acyl, sulfoxyl, sulfonyl, sulfonate, phosphonate, amido, carbamoyl, or a combination comprising at least one of the foregoing substituents.

6. The polymer of claim 4 , wherein the co-monomer has the structure (IX), (X), or (XI):

wherein R is hydrogen, hydroxyl, C 6 -C 12 aryl, C 3 -C 10 cycloalkyl, C 1 -C 12 alkyl, halogen, C 1 -C 12 alkoxy, C 1 -C 12 alkylthio, C 1 -C 12 haloalkyl, C 6 -C 12 haloaryl, pyridyl, cyano, thiocyanato, nitro, amino, C 1 -C 12 alkylamino, C 1 -C 12 aminoalkyl, acyl, sulfonyl, sulfonate, phosphonate, amido, or carbamoyl, carboxylic acid, C 1 -C 12 alkyl carboxylic acid ester, or sulfonic acid (—SO 3 H).

7. The polymer of claim 4 , wherein the co-monomer is

wherein X is C 1 -C 4 alkylene or substituted C 1 -C 4 alkylene; and wherein X 1 is S, O, or N—R 5 , wherein R 5 is hydrogen or C 1 -C 12 alkyl.

8. The polymer of claim 4 , wherein the co-monomer is

wherein X 1 is S, O, or N—R 5 , wherein R 5 is hydrogen or C 1 -C 12 alkyl; and wherein R 3 and R 4 are the same or different, wherein each is hydrogen, hydroxyl, C 6 -C 12 aryl, C 3 -C 10 cycloalkyl, C 1 -C 12 alkyl, halogen, C 1 -C 12 alkoxy, C 1 -C 12 alkylthio, C 1 -C 12 haloalkyl, C 1 -C 12 haloalkoxy, C 6 -C 12 haloaryl, or —C 1 -C 6 alkyl-O—C 1 -C 6 alkyl, or —C 1 -C 6 alkyl-O—C 6 -C 12 aryl.

9. The polymer of claim 4 , wherein the co-monomer is

wherein Q 1 is S or O;

wherein X 1 is S, O, N—R 5 , wherein R 5 is hydrogen or C 1 -C 12 alkyl,

wherein X 2 and X 3 are the same or different and are CH or N, and

wherein R 3 and R 4 are the same or different and wherein each is hydrogen, hydroxyl, C 6 -C 12 aryl, C 3 -C 10 cycloalkyl, C 1 -C 12 alkyl, halogen, C 1 -C 12 alkoxy, C 1 -C 12 alkylthio, C 1 -C 12 haloalkoxy, C 1 -C 12 haloalkyl, C 6 -C 12 haloaryl, —C 1 -C 6 alkyl-O—C 1 -C 6 alkyl, or —C 1 -C 6 alkyl-O—C 6 -C 12 aryl;

wherein X 1 , Q 1 , R 3 , and R 4 are as previously defined, and wherein each occurrence of Q 1 , R 3 , or R 4 may be the same or different;

wherein X 1 is as previously defined;

wherein X 1 , R 3 , and R 4 are as previously defined, and wherein each occurrence of X 1 may be the same or different;

wherein X 1 and X 4 are as previously defined, and wherein each occurrence of X 1 may be the same or different;

wherein X 1 and R 3 are as previously defined, and wherein each occurrence of X 1 or R 3 may be the same or different;

wherein X 1 and R 3 are as previously defined, and wherein each occurrence of X 1 or R 3 may be the same or different;

wherein X 1 is as previously defined, and wherein each occurrence of X 1 may be the same or different, and

wherein E is O or C(R 7 ) 2 , wherein each occurrence of R 7 is an electron withdrawing group;

wherein X 1 , Q 1 , and R 3 are as previously defined, and wherein each occurrence of X 1 , Q 1 , or R 3 may be the same or different;

wherein X 1 and R 3 are as previously defined, and wherein each occurrence of X 1 or R 3 may be the same or different, and

wherein each occurrence of R 8 is hydrogen, C 1 -C 6 alkyl, or cyano;

wherein X 1 , R 3 , and R 8 are as previously defined, wherein each occurrence of X 1 , R 3 , or R 8 may be the same or different, and

wherein each occurrence of Q 3 is independently CH 2 , S, or O;

wherein X 1 and R 3 are as previously defined, wherein each occurrence of X 1 or R 3 may be the same or different, and

wherein Ar is a furan, pyrrole, N-substituted pyrrole, phenyl, biphenyl, thiophene, fluorene, or 9-alkyl-9H-carbazole;

wherein X 1 , Q 1 , R 3 , and Ar are as previously defined, and wherein each occurrence of X 1 , Q 1 , or R 3 may be the same or different;

wherein X 1 , X 4 , Q 1 , and R 3 are as previously defined, and wherein each occurrence of X 1 , Q 1 , or R 3 may be the same or different;

wherein X 1 , X 4 , and R 3 are as previously defined, and wherein each occurrence of X 1 or R 3 may be the same or different;

wherein X 1 and X 4 are as previously defined, and wherein each occurrence of X 1 or X 4 may be the same or different;

wherein X 1 and Q 1 are as previously defined, and wherein each occurrence of Q 1 may be the same or different;

wherein X 1 and Q 1 are as previously defined, and wherein each occurrence of X 1 or Q 1 may be the same or different;

wherein X 1 , R 3 , and Q 1 are as previously defined, and wherein each occurrence of R 3 or Q 1 may be the same or different;

wherein X 1 , R 3 , and Q 1 are as previously defined, and wherein each occurrence of X 1 , R 3 , or Q 1 may be the same or different;

wherein X 1 , R 3 , Q 1 , and Ar are as previously defined, and wherein each occurrence of X 1 , R 3 , or Q 1 may be the same or different;

wherein X 1 , R 3 , and Q 1 are as previously defined, and wherein each occurrence of X 1 , R 3 , or Q 1 may be the same or different;

wherein X 1 , R 3 , and Q 1 are as previously defined, and wherein each occurrence of X 1 , R 3 , or Q 1 may be the same or different; or

a combination comprising at least one of the foregoing co-monomers.

10. The polymer of claim 4 , wherein the co-monomer is 3,4-ethylenedioxythiophene or pyrrole.

11. The polymer of claim 1 , which has been doped with a p-dopant or an n-dopant.

12. The polymer of claim 1 , which is dispersed in an aqueous or a non-aqueous solvent to form a dispersion.

13. The polymer of claim 1 , wherein the polymer has a band gap of below about 1.3 eV.

14. An article comprising the polymer of claim 1 .

15. A process, comprising:

polymerizing a monomeric composition comprising thieno[3,4-b]furan according to the structure (I), (II), or (III):

by electrochemical or chemical reaction to form a polymer, wherein R a is hydrogen, hydroxyl, C 6 -C 12 aryl, C 3 -C 10 cycloalkyl, C 1 -C 12 alkyl, halogen, C 1 -C 12 alkoxy, C 1 -C 12 alkylthio, C 1 -C 12 haloalkyl, C 1 -C 12 haloalkoxy, C 6 -C 12 haloaryl, pyridyl, cyano, thiocyanato, nitro, amino, C 1 -C 12 alkylamino, C 1 -C 12 aminoalkyl, acyl, sulfoxyl, sulfonyl, sulfonate, phosphonate, amido, or carbamoyl.

16. The process of claim 15 , wherein electrochemical reaction is in an electrochemical cell comprising an electrolyte, a working electrode, a counter electrode, and a reference electrode in operable communication.

17. The process of claim 16 , wherein the working electrode is a platinum, gold, or vitreous carbon working electrode, stainless steel and the counter electrode is platinum, stainless steel or gold.

18. The process of claim 16 , wherein the working electrode is a vitreous carbon electrode and the electrolyte is tetrabutylammonium perchlorate/acetonitrile.

19. The process of claim 15 , wherein the electrochemical reaction provides the polymer on an indium tin oxide substrate.

20. The process of claim 15 , further comprising reducing the polymer.