Cross-conjugated polymers for organic electronic devices and related methods

1. A polymer comprising repeating units having the structure:

wherein

D 1 is a first donor segment;

D 2 is a second donor segment, wherein D 2 at each occurrence is selected from the group consisting of triphenylamine, N,N-diphenyl-2-thiophenamine, 9-phenylcarbazole, 9-(2′-thiophene)-carbazole, 4-phenyldithienopyrrole, 4-(2′-thiophene)-dithienopyrrole, 6,12-diphenylindolocarbazole, tetraphenylbiphenyldiamine, and tetraphenylbenzenediamine;

A 1 is an acceptor segment;

B is a π-bridge moiety that conjugates D 2 to A 1 ;

k is 1 or 2; and

n is an integer from 2 to 2000.

2. The polymer of claim 1 , wherein D 1 at each occurrence is selected from the group consisting of substituted or unsubstituted triphenylamine, substituted or unsubstituted fluorene, substituted or unsubstituted indenofluorene, substituted or unsubstituted cyclopentadithiophene, substituted or unsubstituted 2,2′-fluorenebisthiophene, substituted or unsubstituted carbazole, substituted or unsubstituted indolocarbazole, substituted or unsubstituted silafluorene, substituted or unsubstituted silolodithiophene, substituted or unsubstituted dithienopyrrole, and substituted or unsubstituted benzobisthiophene.

3. The polymer of claim 1 , wherein A 1 , A 2 , and A 3 at each occurrence are independently selected from the group consisting of malononitrile, cyano-(3-cyano-4,5,5-trimethyl-5H-furan-2-ylidene)-acetic acid ethyl ester, 2-(3-cyano-4,5,5-trimethyl-5H-furan-2-ylidene)-malononitrile, 1,3-diethyl-2-thioxo-dihydro-pyrimidine-4,6-dione, 2-ethylidene-malononitrile, 1,3-diethyl-5-ethylidene-pyrimidine-2,4,6-trione, 2-(3-cyano-5,5-dimethyl-4-propenyl-5-furan-2-ylidene)-malononitrile, 5-ethylidene-1,3-diphenyl-2-thioxo-dihydro-pyrimidine-4,6-dione, 2-(2-ethylidene-3-oxo-indan-1-ylidene)-malononitrile, 2-[1-(2,3,5,6-tetrafluoro-pyridin-4-yl)-ethylidene]-malononitrile, and cyano-(3-cyano-4,5,5-trimethyl-5-furan-2-ylidene)-acetic acid ethyl ester.

4. The polymer of claim 1 , wherein B at each occurrence is selected from the group consisting of substituted or unsubstituted phenylenevinylene thienylenevinylene, substituted or unsubstituted thienylenevinylene, substituted tetraene, substituted or unsubstituted bithiophene, and substituted or unsubstituted tetrathiophene.

5. A photovoltaic device, comprising:

(a) a hole-collecting electrode;

(b) an electron-collecting electrode; and

(c) a photovoltaic layer intermediate the hole-collecting electrode and the electron-collecting electrode, wherein the photovoltaic layer comprises one or more polymers of claim 1 .

6. The device of claim 5 further comprising a hole-accepting layer intermediate the photovoltaic layer and the hole-collecting electrode.

7. The device of claim 5 further comprising an electron-accepting layer intermediate the photovoltaic layer and the electron-collecting electrode.

8. A solar cell comprising the device of claim 5 .

9. A solar window comprising the device of claim 5 .

10. A photodetector comprising the device of claim 5 .

11. A field-effect transistor device, comprising:

(a) a gate electrode;

(b) a source electrode;

(c) a drain electrode;

(d) an insulating layer intermediate the gate electrode and the source and drain electrodes; and

(e) an active layer intermediate the insulating layer and the source and drain electrodes, wherein the active layer comprises one or more polymers of claim 1 .

12. A field-effect transistor device, comprising:

(a) a gate electrode;

(b) a source electrode;

(c) a drain electrode;

(d) an insulating layer intermediate the gate electrode and the source and drain electrodes; and

(e) an active layer intermediate the source and drain electrodes, wherein the active layer comprises one or more polymers of claim 1 .

13. A photodetector comprising the device of claim 11 .

14. A polymer comprising repeating units having the structure:

wherein

D 1 is a first donor segment;

D 2 is a second donor segment;

A 1 is an acceptor segment;

B is a π-bridge moiety that conjugates D 2 to A 1 , wherein B at each occurrence is selected from the group consisting of substituted or unsubstituted phenylenevinylene thienylenevinylene, substituted or unsubstituted thienylenevinylene, substituted tetraene, substituted or unsubstituted bithiophene, and substituted or unsubstituted tetrathiophene;

k is 1 or 2; and

n is an integer from 2 to 2000.

15. The polymer of claim 14 , wherein D 1 at each occurrence is selected from the group consisting of substituted or unsubstituted triphenylamine, substituted or unsubstituted fluorene, substituted or unsubstituted indenofluorene, substituted or unsubstituted cyclopentadithiophene, substituted or unsubstituted 2,2′-fluorenebisthiophene, substituted or unsubstituted carbazole, substituted or unsubstituted indolocarbazole, substituted or unsubstituted silafluorene, substituted or unsubstituted silolodithiophene, substituted or unsubstituted dithienopyrrole, and substituted or unsubstituted benzobisthiophene.

16. The polymer of claim 14 , wherein A 1 , A 2 , and A 3 at each occurrence are independently selected from the group consisting of malononitrile, cyano-(3-cyano-4,5,5-trimethyl-5H-furan-2-ylidene)-acetic acid ethyl ester, 2-(3-cyano-4,5,5-trimethyl-5H-furan-2-ylidene)-malononitrile, 1,3-diethyl-2-thioxo-dihydro-pyrimidine-4,6-dione, 2-ethylidene-malononitrile, 1,3-diethyl-5-ethylidene-pyrimidine-2,4,6-trione, 2-(3-cyano-5,5-dimethyl-4-propenyl-5-furan-2-ylidene)-malononitrile, 5-ethylidene-1,3-diphenyl-2-thioxo-dihydro-pyrimidine-4,6-dione, 2-(2-ethylidene-3-oxo-indan-1-ylidene)-malononitrile, 2-[1-(2,3,5,6-tetrafluoro-pyridin-4-yl)-ethylidene]-malononitrile, and cyano-(3-cyano-4,5,5-trimethyl-5-furan-2-ylidene)-acetic acid ethyl ester.

17. A photovoltaic device, comprising:

(a) a hole-collecting electrode;

(b) an electron-collecting electrode; and

(c) a photovoltaic layer intermediate the hole-collecting electrode and the electron-collecting electrode, wherein the photovoltaic layer comprises one or more polymers of claim 14 .

18. The device of claim 17 further comprising a hole-accepting layer intermediate the photovoltaic layer and the hole-collecting electrode.

19. The device of claim 17 further comprising an electron-accepting layer intermediate the photovoltaic layer and the electron-collecting electrode.

20. A solar cell comprising the device of claim 17 .

21. A solar window comprising the device of claim 17 .

22. A photodetector comprising the device of claim 17 .

23. A field-effect transistor device, comprising:

(a) a gate electrode;

(b) a source electrode;

(c) a drain electrode;

(d) an insulating layer intermediate the gate electrode and the source and drain electrodes; and

(e) an active layer intermediate the insulating layer and the source and drain electrodes, wherein the active layer comprises one or more polymers of claim 14 .

24. A field-effect transistor device, comprising:

(a) a gate electrode;

(b) a source electrode;

(c) a drain electrode;

(d) an insulating layer intermediate the gate electrode and the source and drain electrodes; and

(e) an active layer intermediate the source and drain electrodes, wherein the active layer comprises one or more polymers of claim 14 .

25. A photodetector comprising the device of claim 23 .