Soluble alternating donor-acceptor conjugated polymer electrochromes

1. An alternating donor-acceptor (DA) n polymer comprising:

a plurality of donor units comprising 3,4-alkylenedioxythiophenes substituted on the alkylene bridge; and

a plurality of acceptor units comprising electron-poor aromatic units or cyanovinylene units alternating with said donor units in one or more polymeric (DA) n sequences of n=4 to 200,000 units, wherein said (DA) n polymer displays a blue or green color in a neutral state and is transmissive in an oxidized state and wherein said (DA) n polymer is soluble in at least one solvent.

2. The (DA) n polymer of claim 1 , wherein said 3,4-alkylenedioxythiophenes substituted on the alkylene bridge comprise:

where x is 0 or 1, y is 0 or 1, and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are independently H, C 1 -C 30 alkyl, C 2 -C 30 alkenyl, C 2 -C 30 alkynyl, C 6 -C 14 aryl, C 7 -C 30 arylalkyl, C 8 -C 30 arylalkenyl, C 8 -C 30 arylalkynyl, hydroxy, C 1 -C 30 alkoxy, C 6 -C 14 aryloxy, C 7 -C 30 arylalkyloxy, C 2 -C 30 alkenyloxy, C 2 -C 30 alkynyloxy, C 8 -C 30 arylalkenyloxy, C 8 -C 30 arylalkynyloxy, CO 2 H, C 2 -C 30 alkylester, C 7 -C 15 arylester, C 8 -C 30 alkylarylester, C 3 -C 30 alkenylester, C 3 -C 30 alkynylester, NH 2 , C 1 -C 30 alkylamino, C 6 -C 14 arylamino, C 7 -C 30 (arylalkyl)amino, C 2 -C 30 alkenylamino, C 2 -C 30 alkynylamino, C 8 -C 30 (arylalkenyl)amino, C 8 -C 30 (arylalkynyl)amino,C 2 -C 30 dialkylamino, C 12 -C 28 diarylamino, C 4 -C 30 dialkenylamino, C 4 -C 30 dialkynylamino, C 7 -C 30 aryl(alkyl)amino, C 7 -C 30 di(arylalkyl)amino, C 8 -C 30 alkyl(arylalkyl)amino, C 15 -C 30 aryl(arylalkyl)amino, C 8 -C 30 alkenyl(aryl)amino, C 8 -C 30 alkynyl(aryl)amino C(O)NH 2 (amido), C 2 -C 30 alkylamido, C 7 -C 14 arylamido, C 8 -C 30 (arylalkyl)amido, C 2 -C 30 dialkylamido, C 12 -C 28 diarylamido, C 8 -C 30 aryl(alkyl)amido, C 15 -C 30 di(arylalkyl)amido, C 9 -C 30 alkyl(arylalkyl)amido, C 16 -C 30 aryl(arylalkyl)amido, thiol, C 1 -C 30 alkyhydroxy, C 6 -C 14 arylhydroxy, C 7 -C 30 arylalkylhydroxy, C 3 -C 30 alkenylhydroxy, C 3 -C 30 alkynylhydroxy, C 8 -C 30 arylalkenylhydroxy, C 8 -C 30 arylalkynylhydroxy, C 3 -C 30 polyether, C 3 -C 30 polyetherester, C 3 -C 30 polyester C 3 -C 30 polyamino, C 3 -C 30 polyaminoamido, C 3 -C 30 polyaminoether, C 3 -C 30 polyaminoester, or C 3 -C 30 polyamidoester.

3. The (DA) n polymer of claim 1 , wherein said acceptor unit comprises: benzo[c][1,2,5]thiadiazole, benzo[c][1,2,5]oxadiazole, quinoxaline, benzo[d][1,2,3]triazole, pyrido[3,4-b]pyrazine, cyanovinylene, thiazolo[5,4-d]thiazole, 1,3,4-thiadiazole, pyrrolo[3,4-c]pyrrole-1,4-dione , 2,2′-bithiazole, [1,2,5]thiadiazolo[3,4-c]pyridine, thieno[3,4-b]pyrazine, [1,2,5]oxadiazolo[3,4-c]pyridine, dicyanovinylene, benzo[1,2-c;4,5-c′]bis[1,2,5]thiadiazole, [1,2,5]thiadiazolo[3,4-g]quinoxaline, 4-dicyanomethylenecyclopentadithiolene, benzo[c]thiophene or any derivative thereof.

4. The (DA) n polymer of claim 1 , wherein said one or more polymeric sequences comprise one or more portions of a block copolymer, graft copolymer, polymer network or super-molecular structure.

5. The (DA) n polymer of claim 1 , wherein the neutral state polymer exhibits a window of transmission in the range 320-560 nm with a maximum transmission at 400 to 500 nm.

6. The (DA) n polymer of claim 5 , wherein light absorbance at maxima of visible bands adjacent to said window of transmission in said neutral state are at least 20% greater than that in a fully oxidized state.

7. The (DA) n polymer of claim 1 , wherein said polymeric sequence comprises:

where R is CH 2 O-n-octyl, CH 2 O-2-ethylhexyl, or CH 2 COO-n-dodecyl and n is 4 to 200,000.

8. The (DA) n polymer of claim 1 , wherein said polymeric sequence comprises:

where R is CH 2 O-n-octyl, CH 2 O-2-ethylhexyl, or CH 2 COO-n-dodecyl and n is 4 to 200,000.

9. A method for preparation of a (DA) n polymer of claim 1 comprising:

combining in one or more solvents a plurality of at least one nucleophilic aromatic monomeric acceptor units that is disubstituted with groups comprising tin, boron, zinc, silicon, or magnesium and a plurality of at least one electrophilic monomeric donor unit comprising a 3,4-alkylenedioxythiophene substituted on the alkylene bridge having a pair of leaving groups; or

combining in one or more solvents a plurality of at least one electrophilic monomeric donor unit comprising a 3,4-alkylenedioxythiophene substituted on the alkylene bridge that is disubstituted with groups comprising tin, boron, zinc, silicon, or magnesium and a plurality of at least one nucleophilic aromatic monomeric acceptor units having a pair of leaving groups;

optionally adding a catalyst; and

cross-coupling said monomeric donor units with said monomeric acceptor units to yield a (DA) n polymer with alternating donor and acceptor units that has a blue or green neutral state and a transmissive oxidized state and is soluble in at least one of said solvents.

10. The method of claim 9 , wherein said monomeric acceptor unit comprises a benzothiadiazole unit or a thienopyrazine unit.

11. The method of claim 9 , wherein said leaving group comprises halogen, triflate, tosylate, nosylate, trifluoroacetate, or mesylate.

12. The method of claim 11 , wherein said halogen comprises bromine.

13. The method of claim 9 , wherein said catalyst comprises a palladium or nickel comprising compound.

14. The method of claim 9 , wherein said cross-coupling comprises a Stille coupling, Kumada coupling, Hiyama coupling, Negishi coupling or inverse Suzuki coupling.

15. The method of claim 9 , wherein said cross-coupling comprises an inverse Suzuki condensation.

16. The method of claim 9 , wherein said cross-coupling comprises a base free inverse Suzuki condensation.