Fused thiophene-based conjugated polymers and their use in optoelectronic devices

1. A polymer comprising as repeating units at least one annulated thienyl-vinylene-thienyl (TVT) unit and at least one other pi-conjugated unit, wherein the annulated TVT unit is selected from the group consisting of:

wherein R 1 and R 2 independently are selected from the group consisting of H, halogen, CN, a C 1-40 alkyl group, a C 2-40 alkenyl group, and a C 1-40 haloalkyl group; and

wherein the other pi-conjugated unit is a conjugated linear linker comprising one or more unsaturated bonds, or a conjugated cyclic linker comprising one or more carbocyclic and/or heterocyclic rings.

2. The polymer of claim 1 , wherein the annulated TVT unit is:

3. The polymer of claim 2 , wherein the annulated TVT unit is present in a first repeating unit of the formula:

wherein:

pi-1 is the annulated TVT unit;

pi-2 is a covalent bond or an optionally substituted conjugated polycyclic moiety; and

Sp 1 , Sp 2 , and Sp 3 independently are a covalent bond or a conjugated spacer group comprising at least one of a conjugated linear linker and an optionally substituted conjugated monocyclic moiety;

provided at least one of pi-2, Sp 1 , Sp 2 , and Sp 3 is not a covalent bond.

4. The polymer of claim 3 , wherein Sp 1 , Sp 2 , and Sp 3 independently are selected from the group consisting of:

and a covalent bond, wherein each Ar independently is an optionally substituted conjugated monocyclic moiety; Z is a conjugated linear linker; and m is 1, 2, 3, 4 or 5.

5. The polymer of claim 4 , wherein each Ar independently is a monocyclic 5- or 6-membered aryl or heteroaryl group optionally substituted with 1-4 R 3 groups, wherein each R 3 independently is selected from the group consisting of a halogen, CN, oxo, ═C(CN) 2 , a C 1-40 alkyl group, a C 1-40 haloalkyl group, a C 1-40 alkoxy group, and a C 1-40 alkylthio group.

6. The polymer of claim 4 , wherein Z is selected from the group consisting of:

wherein each R 4 independently is selected from the group consisting of H, a halogen, CN, a C 1-40 alkyl group, a C 1-40 haloalkyl group, a C 1-40 alkoxy group, and a C 1-40 alkylthio group.

7. The polymer of claim 4 , wherein pi-2 is a conjugated polycyclic moiety 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 polymer of claim 3 having a formula 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, where 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 n is an integer in the range of 3 and 5,000.

9. The polymer of claim 8 , wherein pi-2 is selected from the group consisting of:

wherein R b is a linear or branched C 1-40 alkyl, C 1-40 haloalkyl, C 2-40 alkenyl, or C 2-40 alkynyl group.

10. The polymer of claim 8 , wherein pi-2 is selected from the group consisting of:

wherein R b is a linear or branched C 1-40 alkyl, C 1-40 haloalkyl, C 2-40 alkenyl, or C 2-40 alkynyl group; R d is selected from R, OR, and SR; R is a linear or branched C 1-40 alkyl, C 1-40 haloalkyl, C 2-40 alkenyl, or C 2-40 alkynyl group; and R e is selected from the group consisting of H, F, and Cl.

11. The polymer of claim 3 , wherein the polymer comprises a second repeating unit different from the first repeating unit and the second repeating unit has the formula:

wherein:

pi-1′ is selected from the group consisting of:

wherein R 1 ′ and R 2 ′ independently are selected from the group consisting of H, halogen, CN, a C 1-40 alkyl group, a C 2-40 alkenyl group, and a C 1-40 haloalkyl group;

pi-2′ is a covalent bond or an optionally substituted conjugated polycyclic moiety; and

each of Sp 1 ′, Sp 2 ′, and Sp 3 ′ independently is a covalent bond or a conjugated spacer group having a formula selected from the group consisting of:

wherein each Ar′ independently is an optionally substituted conjugated monocyclic moiety; Z′ is a conjugated linear linker; and m′ is 1, 2, 3 or 4.

12. The polymer of claim 11 , wherein the first repeating unit and the second repeating unit are arranged in an alternating manner.

13. The polymer of claim 11 , where the first repeating unit and the second repeating unit are arranged in a random manner.

14. The polymer of claim 11 having the formula:

wherein n is an integer in the range of 3 to 5,000; x and y are real numbers representing mole fractions, wherein 0.05≦x≦0.95, 0.05≦y≦0.95, and the sum of x and y is 1; and provided Ar is different from Ar′, or R 1 and R 2 are different from R 1 ′ and R 2 ′, or pi-2 is different from pi-2′, or m is different from m′.

15. The polymer of claim 14 having the formula:

wherein:

each R 1 and R 2 independently are selected from the group consisting of H, halogen, CN, a C 1-40 alkyl group, a C 2-40 alkenyl group, and a C 1-40 haloalkyl group;

each R 3 independently is selected from the group consisting of R, OR, and SR;

pi-2 is a conjugated polycyclic moiety 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;

n is an integer in the range of 2 to 10,000;

x and y are real numbers representing mole fractions, wherein 0.05≦x≦0.95, 0.05≦y≦0.95, and the sum of x and y is 1.

16. An organic thin film transistor comprising a polymeric semiconductor component, the polymeric semiconductor component comprising the polymer of claim 2 .

17. An organic photovoltaic device comprising an anode, a cathode, optionally one or more anode interlayers, optionally one or more cathode interlayers, and in between the anode and the cathode a polymeric semiconductor component comprising a blend material, the blend material comprising an electron-acceptor compound and an electron-donor compound, the electron-donor compound being the polymer of claim 2 .

18. The device of claim 17 , wherein the electron-acceptor compound is a fullerene compound.

19. An organic photovoltaic device comprising an anode, a cathode, optionally one or more anode interlayers, optionally one or more cathode interlayers, and in between the anode and the cathode a polymeric semiconductor component comprising a blend material, the blend material comprising an electron-acceptor compound and an electron-donor compound, the electron-acceptor compound being the polymer of claim 2 .

20. The device of claim 17 , wherein the electron-acceptor compound is an electron-transporting polymer.