Polymers containing substituted benzodithiophene units, blends comprising these polymers, and devices comprising these polymers or blends

1. A copolymer comprising structural units of general formula (I)

and an aromatic structural unit selected from the group consisting of 4,5-dihydropyrene derivatives, 4,5,9,10-tetrahydropyrene derivatives, fluorene derivatives, 9,9′-spirobifluorene derivatives, phenanthrene derivatives, 9,10-dihydrophenanthrene derivatives, 5,7-dihydrodibenzoxepine derivatives and cis- and trans-indenofluorene derivatives,

wherein:

X and Y are on each occurrence independently selected from naphthyl, anthracenyl, phenanthrenyl, dihydrophenanthrenyl, biphenyl, terphenyl, fluorenyl, spirobifluorenyl, cis- or trans-indenofluorenyl, truxenyl, isotruxenyl, spirotruxenyl, spiroisotruxenyl, carbazolyl, pyridinyl, quinolinyl, or isoquinolinyl, wherein one or more H atoms are optionally replaced by R, and wherein one of the two groups X or Y is optionally R;

R is identically or differently on each occurrence D, F, Cl, Br, I, N(Ar 1 ) 2 , C(═O)Ar 1 , P(═O)Ar 1 2 , S(═O)Ar 1 , S(═O) 2 Ar 1 , CR 1 ═CR 1 Ar 1 , CN, NO 2 , Si(R 1 ) 3 , B(OR 1 ) 2 , OSO 2 R 1 , a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, each of which is optionally substituted by one or more radicals R 1 , wherein one or more non-adjacent CH 2 groups is optionally replaced by R 1 C═CR 1 , C≡C, Si(R 1 ) 2 , Ge(R 1 ) 2 , Sn(R 1 ) 2 , C═O, C═S, C═Se, C═NR 1 , P(═O)(R 1 ), SO, SO 2 , NR 1 , O, S, or CONR 1 , and wherein one or more H atoms is optionally replaced by F, Cl, Br, I, CN, or NO 2 ;

Ar 1 is identically or differently on each occurrence an aryl or heteroaryl group or an aromatic or heteroaromatic ring system; and

R 1 is identically or differently on each occurrence H, an aliphatic hydrocarbon radical having 1 to 20 C atoms, or an aromatic hydrocarbon radical having 6 to 20 C atoms;

wherein the H atom present in each case in one or both of the thiophene rings is optionally replaced by R; and wherein the dashed lines, represent the bonds to the adjacent structural units in the copolymer.

2. The copolymer of claim 1 , wherein X and/or Y are substituted by one or more linear alkyl or alkoxy radicals having 1 to 12 C atoms, branched alkyl or alkoxy radicals having 3 to 12 C atoms or cyclic alkyl or alkoxy radicals having 6 to 12 C atoms, or by one or more aryl, heteroaryl, aryloxy or heteroaryloxy groups.

3. The copolymer of claim 1 , wherein the structural unit of the formula (I) is present in the range from 0.2 to 80 mol %.

4. The copolymer of claim 3 , wherein said further structural unit is a hole-injection, hole-transport, hole-blocking, electron-injection, electron-transport, electron-blocking, emitter, exciton-generating unit, backbone unit, or combination thereof.

5. The copolymer of claim 3 , further comprising structural units with derivatized molecular groups, the molecular groups selected from the group consisting of triarylamine, benzidine, tetraaryl-para-phenylenediamine, triarylphosphine, phenothiazine, phenoxazine, dihydrophenazine, thianthrene, dibenzo-para-dioxin, phenoxathiyne, carbazole, azulene, thiophene, pyrrole and furan.

6. The copolymer of claim 5 having a HOMO greater than −5.8 eV as measured against vacuum level.

7. A blend comprising the copolymer of claim 1 and a different polymer, oligomer, dendrimer, or low-molecular-weight compound.

8. An organic electronic device comprising the blend of claim 7 .

9. A formulation comprising the blend of claim 7 and one or more solvents.

10. An organic electronic device comprising one or more layers, wherein at least one layer comprises the blend of claim 7 .

11. The organic electronic device of claim 10 , wherein said one or more layers comprise one or more hole-injection layer, hole-transport layer, hole-blocking layer, electron-injection layer, electron-transport layer, electron-blocking layer, charge-generation or emitter layer, a layer which comprises exciton-generating units, or combinations thereof.

12. The organic electronic device according to claim 10 , wherein said organic electronic device is an organic electroluminescent device, a polymeric electroluminescent device, an organic integrated circuit, an organic field-effect transistor, an organic thin-film transistor, an organic light-emitting transistor, an organic solar cell, an organic optical detector, an organic photoreceptor, an organic field-quench device, a light-emitting electrochemical cell, or an organic laser diode.

13. An organic electronic device comprising the copolymer of claim 1 .

14. A formulation comprising the polymer of claim 1 and one or more solvents.

15. An organic electronic device comprising one or more layers, wherein at least one layer comprises the copolymer of claim 1 .

16. The organic electronic device of claim 15 , wherein said one or more layers comprise one or more hole-injection layer, hole-transport layer, hole-blocking layer, electron-injection layer, electron-transport layer, electron-blocking layer, charge-generation or emitter layer, a layer which comprises exciton-generating units, or combinations thereof.

17. The organic electronic device according to claim 15 , wherein said organic electronic device is an organic electroluminescent device, a polymeric electroluminescent device, an organic integrated circuit, an organic field-effect transistor, an organic thin-film transistor, an organic light-emitting transistor, an organic solar cell, an organic optical detector, an organic photoreceptor, an organic field-quench device, a light-emitting electrochemical cell, or an organic laser diode.

18. An organic electroluminescent device comprising the copolymer of claim 1 .

19. The copolymer of claim 1 wherein at least one of X and Y is selected from naphthyl or anthracenyl.

20. An organic electronic device comprising one or more layers, wherein at least one layer comprises the copolymer of claim 19 .

21. The copolymer of claim 19 , further comprising structural units of group 1 that include molecular groups selected from the group consisting of triarylamine, benzidine, tetraaryl-para-phenylenediamine, triarylphosphine, phenothiazine, phenoxazine, dihydrophenazine, thianthrene, dibenzo-para-dioxin, phenoxathiyne, carbazole, azulene, thiophene, pyrrole and furan.

22. The copolymer of claim 1 , wherein the structural units of general formula (I) is present in the copolymer from 0.5 to 60 mol %, and the copolymer has a molecular weight in the range from 10,000 to 2,000,000 g/mol, as determined from gel permeation chromatography.

23. The copolymer of claim 1 , wherein the aromatic structural unit is part of the copolymer backbone.