Conjugated polymers

1. A polymer comprising one or more units of formula I

wherein the individual radicals have the following meanings:

X and Y independently of each other, and on each occurrence identically or differently, C(R 1 R 2 ), C═C(R 1 R 2 ), Si(R 1 R 2 ), Ge(R 1 R 2 ), C(═O) or NR 1 ,

A 1 ,

A 2 on each occurrence identically or differently

A 3 on each occurrence identically or differently

provided that A 1 , A 2 and A 3 do not at the same time denote a benzene ring,

V CR 1 or N,

W O, S or Se,

R 1 and R 2 independently of each other H, straight-chain, branched or cyclic alkyl with 1 to 30 C atoms, in which one or more CH 2 groups are optionally replaced by —O—, —S—, —C(═O)—, —C(═S)—, —C(═O)—O—, —O—C(═O)—, —NR 0 —, —SiR 0 R 00 —, —CF 2 —, —CHR 0 ═CR 00 —, —CY 1 ═CY 2 — or —C≡C— in such a manner that O and/or S atoms are not linked directly to one another, and in which one or more H atoms are optionally replaced by F, Cl, Br, I or CN, or denote aryl, heteroaryl, aryloxy or heteroaryloxy with 4 to 20 ring atoms which is optionally substituted,

Y 1 and Y 2 independently of each other H, F, Cl or CN,

R 0 and R 00 independently of each other H or optionally substituted C 1-40 carbyl or hydrocarbyl.

2. The polymer according to claim 1 , characterized in that V in formula I denotes CH.

3. The polymer according to claim 1 , characterized in that W in formula I denotes S.

4. The polymer according to claim 1 , characterized in that A 1 in formula I is selected from the following groups

5. The polymer according to claim 1 , characterized in A 2 in formula I is selected from the following groups

6. The polymer according to claim 1 , characterized in A 3 in formula I is selected from the following groups

7. The polymer according to claim 1 , characterized in the units of formula I are selected from the following subformulae

wherein X and Y have the meanings given in formula I.

8. A polymer according to claim 7 , wherein X and Y independently denote CR 1 R 2 .

9. The polymer according to claim 1 , characterized in that in the units of formula I, R 1 and R 2 denote straight-chain, branched or cyclic alkyl with 1 to 30 C atoms which is unsubstituted or substituted by one or more F atoms, or R 1 and R 2 denote aryl, heteroaryl, aryloxy or heteroaryloxy, each of which is optionally fluorinated, alkylated or alkoxylated and has 4 to 30 ring atoms.

10. The polymer according to claim 1 , characterized in that it comprises one or more units of formula IIa or IIb

—[(Ar 1 ) a -(U) b -(Ar 2 ) c —(Ar 3 ) d ]-  IIa

-[(U) b -(Ar 1 ) a -(U) b -(Ar 2 ) c —(Ar 3 ) d ]-  IIb

wherein

U is a unit of formula I,

Ar 1 , Ar 2 , Ar 3 are, on each occurrence identically or differently, and independently of each other, aryl or heteroaryl that is different from U has 5 to 30 ring atoms and is optionally substituted by one or more groups R S ,

R S is on each occurrence identically or differently F, Br, Cl, —CN, —NC, —NCO, —NCS, —OCN, —SCN, —C(O)NR 0 R 00 , —C(O)X 0 , —C(O)R 0 , —NH 2 , —NR 0 R 00 , —SH, —SR 0 , —SO 3 H, —SO 2 R 0 , —OH, —NO 2 , —CF 3 , —SF 5 , optionally substituted silyl, carbyl or hydrocarbyl with 1 to 40 C atoms that is optionally substituted and optionally comprises one or more hetero atoms,

R 0 and R 00 are independently of each other H or optionally substituted C 1-40 carbyl or hydrocarbyl,

X 0 is halogen,

a, b, c are on each occurrence identically or differently 0, 1 or 2,

d is on each occurrence identically or differently 0 or an integer from 1 to 10,

wherein the polymer comprises at least one repeating unit of formula IIa or IIb wherein b is at least 1.

11. A polymer according to claim 10 , wherein X 0 is F, Cl or Br.

12. The polymer according to claim 10 , characterized in that it additionally comprises one or more repeating units selected of formula IIIa or IIIb

—[(Ar 1 ) a -(A c ) b -(Ar 2 ) c —(Ar 3 ) d ]-  IIIa

-[(A c ) b -(Ar 1 ) a -(A c ) b -(Ar 2 ) c —(Ar 3 ) d ]-  IIIb

wherein Ar 1 , Ar 2 , Ar 3 , a, b, c and d are as defined in claim 10 , and A c is an aryl or heteroaryl group that is different from U and Ar 1-3 , has 5 to 30 ring atoms, is optionally substituted by one or more groups R S as defined in claim 10 , and is selected from aryl or heteroaryl groups having electron acceptor properties, wherein the polymer comprises at least one repeating unit of formula IIIa or IIIb wherein b is at least 1.

13. The polymer according to claim 12 , wherein A c and/or Ar 3 denotes aryl or heteroaryl selected from the group consisting of the following formulae

wherein one of X 11 and X 12 is S and the other is Se, and R 11 , R 12 , R 13 , R 14 and R 15 independently of each other denote H or have one of the meanings of R S .

14. The polymer according to claim 1 , characterized in that it is selected of formula IV:

* (A) x -(B) y -(C) z n *  IV

wherein

A, B, C independently of each other denote a distinct unit of formula I,

x is >0 and ≤1,

y is ≥0 and <1,

z is ≥0 and <1,

x+y+z is 1, and

n is an integer >1.

15. The polymer according to claim 14 , characterized in that it is selected of formula V

R 5 -chain-R 6   V

wherein “chain” is a polymer chain selected of formulae IV as defined in claim 14 , R 5 and R 6 are independently of each other H, F, Br, Cl, I, —CN, —NC, —NCO, —NCS, —OCN, —SCN, —C(O)NR 0 R 00 , —C(O)X 0 , —C(O)R 0 , —NH 2 , —NR 0 R 00 , —SH, —SR 0 , —SO 3 H, —SO 2 R 0 , —OH, —NO 2 , —CF 3 , —SF 5 , optionally substituted silyl, carbyl or hydrocarbyl with 1 to 40 C atoms that is optionally substituted and optionally comprises one or more hetero atoms, —CH 2 Cl, —CHO, —CR′, CR″ 2 , —SiR′R″R′″, —SiR′X′X″, —SiR′R″X′, —SnR′R″R′″, —BR′R″, —B(OR′)(OR″), —B(OH) 2 , —O—SO 2 —R′, —C≡CH, —C≡C—SiR′ 3 , —ZnX′, or an endcap group, wherein X 0 , and X″ denote halogen, R′, R″ and W′ independently of each other are H or optionally substituted C 1-40 carbyl or hydrocarbyl, and two of R′, R″ and W′ may also form a ring together with the hetero atom to which they are attached.

16. The polymer according to claim 1 , characterized in that it is selected from the following formulae

*-[(Ar 1 -U-Ar 2 ) x —(Ar 3 ) y ] n -*  IVa

*-[(Ar 1 -U-Ar 2 ) x —(Ar 3 —Ar 3 ) y ] n -*  IVb

*-[(Ar 1 -U-Ar 2 ) x —(Ar 3 —Ar 3 —Ar 3 ) y ] n -*  IVc

*-[(Ar 1 ) a -(U) b -(Ar 2 ) c —(Ar 3 ) d ] n -*  IVd

*-([(Ar 1 ) a -(U) b -(Ar 2 ) c —(Ar 3 ) d ] x —[(Ar 1 ) a -(A c ) b -(Ar 2 ) c —(Ar 3 ) d ] y ) n -*  IVe

*-[(U-Ar 1 -U) x -(Ar 2 —Ar 3 ) y ] n -*  IVf

*-[(U-Ar 1 -U) x -(Ar 2 —Ar 3 —Ar 2 ) y ] n -*  IVg

*-[(U) b -(Ar 1 ) a -(U) b -(Ar 2 ) c ] n -*  IVh

*-([(U) b -(Ar 1 ) a -(U) b -(Ar 2 ) c ] x -[(A c ) b -(Ar 1 ) a -(A c ) b -(Ar 2 ) d ] y ) n -*   IVi

*-[(U-Ar 1 ) x -(U-Ar 2 ) y -(U-Ar 3 ) z ]-*  IVk

wherein

U is a unit of formula I,

Ar 1 , Ar 2 , Ar 3 are, on each occurrence identically or differently, and independently of each other, aryl or heteroaryl that is different from U has 5 to 30 ring atoms and is optionally substituted by one or more groups R S ,

a, b, c are on each occurrence identically or differently 0, 1 or 2,

d is on each occurrence identically or differently 0 or an integer from 1 to 10,

A c is an aryl or heteroaryl group that is different from U,

Ar 1-3 has 5 to 30 ring atoms, is optionally substituted by one or more groups R S , where R S is on each occurrence identically or differently F, Br, Cl, —CN, —NC, —NCO, —NCS, —OCN, —SCN, —C(O)NR 0 R 00 , —C(O)X 0 , —C(O)R 0 , —NH 2 , —NR 0 R 00 , —SH, —SR 0 , —SO 3 H, —SO 2 R 0 , —OH, —NO 2 , —CF 3 , —SF 5 , optionally substituted silyl, carbyl or hydrocarbyl with 1 to 40 C atoms that is optionally substituted and optionally comprises one or more hetero atoms, wherein R 0 and R 00 are independently of each other H or optionally substituted C 1-40 carbyl or hydrocarbyl,

R 0 and R 00 are independently of each other H or optionally substituted C 1-40 carbyl or hydrocarbyl,

X 0 is halogen,

x is >0 and ≤1,

Y is ≥0 and <1,

z is ≥0 and <1,

x+y+z is 1, and

n is an integer >1,

wherein these polymers can be alternating or random copolymers, and wherein in formula IVd and IVe in at least one of the repeating units [(Ar 1 ) a -(U) b -(Ar 2 ) c -(Ar 3 ) d ] and in at least one of the repeating units [(Ar 1 ) a -(A c ) b -(Ar 2 ) c -(Ar 3 ) d ], b is at least 1 and wherein in formula IVh and IVi in at least one of the repeating units [(U) b -(Ar 1 ) a -(U) b -(Ar 2 ) d ] and in at least one of the repeating units [(U) b -(Ar 1 ) a -(U) b -(Ar 2 ) d ], b is at least 1.

17. A polymer according to claim 16 , wherein X 0 is F, Cl or Br.

18. The polymer according to claim 1 , wherein one or more of Ar 1 , Ar 2 and Ar 3 denote aryl or heteroaryl selected from the group consisting of the following formulae

wherein one of X 11 and X 12 is S and the other is Se,

R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 independently of each other denote H, F, Br, Cl, —CN, —NC, —NCO, —NCS, —OCN, —SCN, —C(O)NR 0 R 00 , —C(O)X 0 , —C(O)R 0 , —NH 2 , —NR 0 R 00 , —SH, —SR 0 , —SO 3 H, —SO 2 R 0 , —OH, —NO 2 , —CF 3 , —SF 5 , optionally substituted silyl, carbyl or hydrocarbyl with 1 to 40 C atoms that is optionally substituted and optionally comprises one or more hetero atoms, X 0 is halogen and

R 0 and R 00 are independently of each other H or optionally substituted C 1-40 carbyl or hydrocarbyl.

19. A mixture or polymer blend comprising one or more polymers according to claim 1 and one or more compounds or polymers having semiconducting, charge transport, hole/electron transport, hole/electron blocking, electrically conducting, photoconducting or light emitting properties.

20. The mixture or polymer blend according to claim 19 , characterized in that it further comprises one or more n-type organic semiconductor compounds.

21. The mixture or polymer blend according to claim 20 , characterized in that the n-type organic semiconductor compound is a fullerene or substituted fullerene.

22. A formulation comprising a mixture or polymer blend according to claim 19 and one or more solvents.

23. A formulation comprising one or more polymers according to claim 1 , and one or more solvents.

24. A charge transport, semiconducting, electrically conducting, photoconducting or light emitting material in an optical, electrooptical, electronic, electroluminescent or photoluminescent device, or in a component of such a device, or in an assembly comprising such a device or component, which comprises a polymer according to claim 1 .

25. A charge transport, semiconducting, electrically conducting, photoconducting or light emitting material comprising a polymer according to claim 1 .

26. An optical, electrooptical, electronic, electroluminescent or photoluminescent device, or a component thereof, or an assembly comprising it, which comprises a charge transport, semiconducting, electrically conducting, photoconducting or light emitting material which comprises a polymer according to claim 1 .

27. A device, a component thereof, or an assembly comprising it according to claim 26 , wherein the device is selected from organic field effect transistors (OFET), thin film transistors (TFT), organic light emitting diodes (OLED), organic light emitting transistors (OLET), organic photovoltaic devices (OPV), organic photodetectors (OPD), organic solar cells, laser diodes, Schottky diodes, and photoconductors, the component is selected from charge injection layers, charge transport layers, interlayers, planarising layers, antistatic films, polymer electrolyte membranes (PEM), conducting substrates, and conducting patterns, and the assembly is selected from integrated circuits (IC), radio frequency identification (RFID) tags or security markings or security devices containing them, flat panel displays or backlights thereof, electrophotographic devices, electrophotographic recording devices, organic memory devices, sensor devices, biosensors and biochips.

28. The device according to claim 27 , which is an OFET, bulk heterojunction (BHJ) OPV device or inverted BHJ OPV device.

29. A process of preparing a polymer according to claim 1 , which comprises coupling one or more monomers of formula VIa or VIb

R 7 —(Ar 1 ) a -U-(Ar 2 ) c —R 8   VIa

R 7 -U-(Ar 1 ) a -U-R 8   VIb

wherein a and c are identically or differently 0, 1 or 2,

U is a unit of formula I,

Ar 1 , Ar 2 , Ar 3 are, on each occurrence identically or differently, and independently of each other, aryl or heteroaryl that is different from U has 5 to 30 ring atoms and is optionally substituted by one or more groups R S ,

R S is on each occurrence identically or differently F, Br, Cl, —CN, —NC, —NCO, —NCS, —OCN, —SCN, —C(O)NR 0 R 00 , —C(O)X°, —C(O)R 0 , —NH 2 , —NR 0 R 00 , —SH, —SR 0 , —SO 3 H, —SO 2 R 0 , —OH, —NO 2 , —CF 3 , —SF 5 , optionally substituted silyl, carbyl or hydrocarbyl with 1 to 40 C atoms that is optionally substituted and optionally comprises one or more hetero atoms,

R 0 and R 00 are independently of each other H or optionally substituted C 1-40 carbyl or hydrocarbyl,

R 7 and R 8 are selected from the group consisting of Cl, Br, I, O-tosylate, O-triflate, O-mesylate, O-nonaflate, —SiMe 2 F, —SiMeF 2 , —O—SO 2 Z 1 , —B(OZ 2 ) 2 , —CZ 3 ═C(Z 3 ) 2 , —C≡CH, —C≡CSi(Z 1 ) 3 , —ZnX 0 and —Sn(Z 4 ) 3 , wherein X 0 is halogen, and

Z 1-4 are selected from the group consisting of alkyl and aryl, each being optionally substituted, and two groups Z 2 may also together form a cyclic group

with each other and/or with one or more monomers selected from the following formulae

R 7 —(Ar 1 ) a -A c -(Ar 2 ) c —R 8   VIII

R 7 —Ar 1 —R 8   IX

R 7 —Ar 3 —R 8   X

wherein Ar 3 is independently as defined for Ar 1 , A c is an aryl or heteroaryl group that is different from U and Ar 1-3 , has 5 to 30 ring atoms, is optionally substituted by one or more groups R S , and R 7 and R 8 are selected from O-tosylate, O-triflate, O-mesylate, O-nonaflate, —SiMe 2 F, —SiMeF 2 , —O—SO 2 Z 1 , —CZ 3 ═C(Z 3 ) 2 , —C≡CH, —C≡CSi(Z 1 ) 3 , —ZnX 0 , Cl, Br, I, —B(OZ 2 ) 2 and —Sn(Z 4 ) 3 , in an aryl-aryl coupling reaction.

30. A polymer according to claim 1 , wherein:

R 1 and R 2 independently of each other are H, straight-chain, branched or cyclic alkyl with 1 to 30 C atoms, in which one or more CH 2 groups are optionally replaced by —O—, —S—, —C(═O)—, —C(═S)—, —C(═O)—O—, —O—C(═O)—, —NR 0 —, —SiR 0 R 00 —, —CF 2 —, —CHR 0 ═CR 00 —, —CY 1 ═CY 2 — or —C≡C— in such a manner that O and/or S atoms are not linked directly to one another, and in which one or more H atoms are optionally replaced by F, Cl, Br, I or CN, or denote aryl, heteroaryl, aryloxy or heteroaryloxy with 4 to 20 ring atoms which is optionally substituted by halogen or by one or more of the aforementioned straight-chain, branched or cyclic alkyl groups, and

R 0 and R 00 independently of each other are H or alkyl with 1 to 12 C-atoms.

31. A polymer according to claim 1 , wherein R 1 and R 2 denote straight-chain, branched or cyclic alkyl with 1 to 30 C atoms which is unsubstituted or substituted by one or more F atoms, or R 1 and R 2 denote aryl, heteroaryl, aryloxy or heteroaryloxy, each of which is optionally fluorinated, alkylated or alkoxylated and has 4 to 30 ring atoms.

32. A formulation comprising one or more polymers according to claim 1 and one or more organic solvents.

33. A monomer of formula VIa or VIb

R 7 —(Ar 1 ) a -U-(Ar 2 ) c —R 8   VIa

R 7 -U-(Ar 1 ) a -U-R 8   VIb

wherein a and c are identically or differently 0, 1 or 2,

U is a unit of formula I,

wherein the individual radicals have the following meanings:

X and Y independently of each other, and on each occurrence identically or differently, C(R 1 R 2 ), C=C(R 1 R 2 ), Si(R 1 R 2 ), Ge(R 1 R 2 ), C(=O) or NR 1 ,

A 1

A 2 on each occurrence identically or differently

A 3 on each occurrence identically or differently

Provided that A 1 , A 2 and A 3 do not at the same time denote a benzene ring,

V CR 1 or N,

W O, S or Se,

R 1 and R 2 independently of each other H, straight-chain, branched or cyclic alkyl with 1 to 30 C atoms, in which one or more CH 2 groups are optionally replaced by —O—, —S—, —C(=O)—, —C(=S)—, —(C=O)—O—, —O—C(=O)—, —NR 0 —, SiR 0 R 00 —, —CF 2 —, —CHR 0 =CR 00 —, —CY 1 =CY 2 — or —C≡C— in such a manner that O and/or S atoms are not linked directly to one another, and in which one or more H atoms are optionally replaced by F, Cl, Br, I or CN, or denote aryl, heteroaryl, aryloxy or heteroaryloxy with 4 to 20 ring atoms which is optionally substituted,

Y 1 and Y 2 independently of each other H, F, Cl or CN,

Ar 1 , Ar 2 , Ar 3 are, on each occurrence identically or differently, and independently of each other, aryl or heteroaryl that is different from U has 5 to 30 ring atoms and is optionally substituted by one or more groups R S ,

R S is on each occurrence identically or differently F, Br, Cl, —CN, —NC, —NCO, —NCS, —OCN, —SCN, —C(O)NR 0 R 00 , —C(O)X 0 , —C(O)R 0 , —NH 2 , —NR 0 R 00 , —SH, —SR 0 , —SO 3 H, —SO 2 R 0 , —OH, —NO 2 , —CF 3 , —SF 5 , optionally substituted silyl, carbyl or hydrocarbyl with 1 to 40 C atoms that is optionally substituted and optionally comprises one or more hetero atoms,

R 0 and R 00 are independently of each other H or optionally substituted C 1-40 carbyl or hydrocarbyl,

R 7 and R 8 are selected from the group consisting of Cl, Br, I, O-tosylate, O-triflate, O-mesylate, O-nonaflate, —SiMe 2 F, —SiMeF 2 , —O—SO 2 Z 1 , —B(OZ 2 ) 2 , —CZ 3 ═C(Z 3 ) 2 , —C≡CH, —C≡CSi(Z 1 ) 3 , —ZnX 0 and —Sn(Z 4 ) 3 , wherein X° is halogen, and

Z 1-4 are selected from the group consisting of alkyl and aryl, each being optionally substituted, and two groups Z 2 may also together form a cyclic group.

34. The monomer according to claim 33 , which is selected from the following formulae

R 7 —Ar 1 -U-Ar 2 —R 8   VI1

R 7 -U-R 8   VI2

R 7 —Ar 1 -U-R 8   VI3

R 7 -U-Ar 2 —R 8   VI4

R 7 -U-Ar 1 -U-R 8   VI5

wherein U, Ar 1 , Ar 2 , R 7 and R 8 are as defined in claim 25 .

35. A monomer according to claim 33 , wherein X 0 is F, Cl or Br.