ORGANIC SEMICONDUCTORS

Abstract

The invention relates to novel compounds containing one or more benzo[1,2-d;4,5-d]bisthiazole-4,8-diyl (BBT) units, to methods for their preparation and educts or intermediates used therein, to mixtures and formulations containing them, to the use of the compounds, mixtures and formulations as organic semiconductors in organic electronic (OE) devices, especially in organic photovoltaic (OPV) devices and organic photodetectors (OPD), and to OE, OPV and OPD devices comprising these compounds, mixtures or formulations.

Claims

1. A compound comprising one or more divalent heteroarylene units of formula I ##STR00098## wherein the individual radicals, independently of each other and on each occurrence identically or differently, have the following meanings R.sup.1, R.sup.2 H, halogen, CN, straight-chain, branched or cyclic alkyl with 1 to 30, preferably 1 to 20, C atoms, in which one or more CH.sub.2 groups are optionally replaced by O, S, C(?O), C(?S), C(?O)O, OC(?O), NR.sup.0, SiR.sup.0R.sup.00, CF.sub.2, CR.sup.0?CR.sup.00, CY.sup.1?CY.sup.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, and in which one or more CH.sub.2 or CH.sub.3 groups are optionally replaced by a cationic or anionic group, or aryl, heteroaryl, aryloxy or heteroaryloxy, wherein each of the aforementioned cyclic groups has 5 to 20 ring atoms, is mono- or polycyclic, does optionally contain fused rings, and is unsubstituted or substituted by one or more identical or different groups L, L F, Cl, CN, NC, NCO, NCS, OCN, SCN, R.sup.0, OR.sup.0, SR.sup.0, C(?O)X.sup.0, C(?O)R.sup.0, C(?O)OR.sup.0, OC(?O)R.sup.0, NH.sub.2, NHR.sup.0, NR.sup.0R.sup.00, C(?O)NHR.sup.0, C(?O)NR.sup.0R.sup.00, SO.sub.3H, SO.sub.2R.sup.0, OH, NO.sub.2, CF.sub.3, SF.sub.5, or optionally substituted silyl, or carbyl or hydrocarbyl with 1 to 20 C atoms that is optionally substituted and optionally comprises one or more hetero atoms Y.sup.1, Y.sup.2 H, F, Cl or CN, X.sup.0 halogen, R.sup.0, R.sup.00 H or straight-chain or branched alkyl with 1 to 20 C atoms that is optionally fluorinated, and further comprising one or more arylene or heteroarylene units that have from 5 to 20 ring atoms, are mono- or polycyclic, do optionally contain fused rings, are unsubstituted or substituted by one or more identical or different groups L, and are either selected of formula I or are structurally different from formula I, wherein all the aforementioned units are directly connected to each other, and wherein the compound is a conjugated polymer, or comprises in total more than three arylene or heteroarylene units, or comprises at least one arylene or heteroarylene unit that is different from ethylenedioxythiophene.

2. A compound according to claim 1, wherein R.sup.1 and R.sup.2 in the units of formula I are selected from the group consisting of R, OR and SR, wherein R is straight-chain or branched alkyl with 1 to 20 C atoms which unsubstituted or substituted by one or more F atoms.

3. A compound according to claim 1, wherein R.sup.1 and R.sup.2 in the units of formula I are selected from the group consisting of C(?O)R, C(?O)OR, OC(?O)R, C(?O)NHR and C(?O)NRR.sup.n, wherein R and R.sup.n are independently of each other straight-chain or branched alkyl with 1 to 20 C atoms, which is unsubstituted or substituted by one or more F atoms.

4. The compound according to claim 1, which is a conjugated polymer comprising one or more units of formula I as defined in claim 1, and further comprising one or more arylene or heteroarylene units that have from 5 to 20 ring atoms, are mono- or polycyclic, do optionally contain fused rings, are unsubstituted or substituted by one or more identical or different groups L, and are either selected of formula I or are structurally different from formula I, and wherein all the aforementioned units are directly connected to each other.

5. A compound of claim 4, which comprises one or more repeating units of formula II1 or II2, and optionally one or more repeating units of formula II3:
(Ar.sup.1).sub.aU(Ar.sup.2).sub.b(Ar.sup.3).sub.c(Ar.sup.4).sub.dII1
(Ar.sup.1).sub.a(Ar.sup.2).sub.bU(Ar.sup.3).sub.c(Ar.sup.4).sub.dII2
(Ar.sup.1).sub.a(Ar.sup.2).sub.b(Ar.sup.3).sub.c(Ar.sup.4).sub.dII3 wherein the individual radicals, independently of each other and on each occurrence identically or differently, have the following meanings U a unit of formula I, ##STR00099## wherein the individual radicals, independently of each other and on each occurrence identically or differently, have the following meanings R.sup.1, R.sup.2 H, halogen, CN, straight-chain, branched or cyclic alkyl with 1 to 30, preferably 1 to 20, C atoms, in which one or more CH.sub.2 groups are optionally replaced by O, S, C(?O), C(?S), C(?O)O, OC(?O), NR.sup.0, SiR.sup.0R.sup.00, CF.sub.2, CR.sup.0?CR.sup.00, CY.sup.1?CY.sup.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, and in which one or more CH.sub.2 or CH.sub.3 groups are optionally replaced by a cationic or anionic group, or aryl, heteroaryl, aryloxy or heteroaryloxy, wherein each of the aforementioned cyclic groups has 5 to 20 ring atoms, is mono- or polycyclic, does optionally contain fused rings, and is unsubstituted or substituted by one or more identical or different groups L, L F, Cl, CN, NC, NCO, NCS, OCN, SCN, R.sup.0, OR.sup.0, SR.sup.0, C(?O)X.sup.0, C(?O)R.sup.0, C(?O)OR.sup.0, OC(?O)R.sup.0, NH.sub.2, NHR.sup.0, NR.sup.0R.sup.00, C(?O)NHR.sup.0, C(?O)NR.sup.0R.sup.00, SO.sub.3H, SO.sub.2R.sup.0, OH, NO.sub.2, CF.sub.3, SF.sub.5, or optionally substituted silyl, or carbyl or hydrocarbyl with 1 to 20 C atoms that is optionally substituted and optionally comprises one or more hetero atoms Y.sup.1, Y.sup.2 H, F, Cl or CN, X.sup.0 halogen, R.sup.0, R.sup.00 H or straight-chain or branched alkyl with 1 to 20 C atoms that is optionally fluorinated, Ar.sup.1-4 arylene or heteroarylene that has 5 to 20 ring atoms, is mono- or polycyclic, does optionally contain fused rings, is unsubstituted or substituted by one or more identical or different groups L, and is different from formula I, a, b, c, d 0 or 1, wherein in formula II3 a+b+c+d?1.

6. A compound according to claim 5, which is selected of formula III:
*?(A).sub.x-(B).sub.y?.sub.n* III wherein A is a unit of formula I, II1 or II2 as defined in claim 5, B is a unit of formula I, II1, II2 or II3 as defined in claim 5, x is >0 and ?1, y is ?0 and <1, x+y is 1, and n is an integer ?5.

7. A compound according to claim 1 which is selected from the following formulae ##STR00100## wherein R.sup.1 and R.sup.2 have the meanings of H, halogen, CN, straight-chain, branched or cyclic alkyl with 1 to 30, preferably 1 to 20, C atoms, in which one or more CH.sub.2 groups are optionally replaced by O, S, C(?O), C(?S), C(?O)O, OC(?O), NR.sup.0, SiR.sup.0R.sup.00, CF.sub.2, CR.sup.0?CR.sup.00, CY.sup.1?CY.sup.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, and in which one or more CH.sub.2 or CH.sub.3 groups are optionally replaced by a cationic or anionic group, or aryl, heteroaryl, aryloxy or heteroaryloxy, wherein each of the aforementioned cyclic groups has 5 to 20 ring atoms, is mono- or polycyclic, does optionally contain fused rings, and is unsubstituted or substituted by one or more identical or different groups L, where L is F, Cl, CN, NC, NCO, NCS, OCN, SCN, R.sup.0, OR.sup.0, SR.sup.0, C(?O)X.sup.0, C(?O)R.sup.0, C(?O)OR.sup.0, OC(?O)R.sup.0, NH.sub.2, NHR.sup.0, NR.sup.0R.sup.00, C(?O)NHR.sup.0, C(?O)NR.sup.0R.sup.00, SO.sub.3H, SO.sub.2R.sup.0, OH, NO.sub.2, CF.sub.3, SF.sub.5, or optionally substituted silyl, or carbyl or hydrocarbyl with 1 to 20 C atoms that is optionally substituted and optionally comprises one or more hetero atoms Y.sup.1, Y.sup.2 are independently H, F, Cl or CN, X.sup.0 is halogen, and R.sup.0, R.sup.00 are independently H or straight-chain or branched alkyl with 1 to 20 C atoms that is optionally fluorinated, R.sup.3 and R.sup.4 have one of the meanings of R.sup.1, Ar.sup.1, Ar.sup.2, Ar.sup.3, Ar.sup.4, are independently arylene or heteroarylene that has 5 to 20 ring atoms, is mono- or polycyclic, does optionally contained fused rings, is unsubstituted or substituted by one or more identical or different groups L, a, b, c and d 0 or 1, wherein a+b+c+d?1, and x is >0 and ?1, y is ?0 and <1, x+y is 1, and n is an integer ?5.

8. A compound of formula IV
R.sup.5-chain-R.sup.6 IV wherein chain denotes a polymer chain selected from formulae III and III1-III5 ##STR00101## wherein in formula III, A is a unit of formula I, II1 or II2, B is a unit of formula I, II1, II2 or II3, x is >0 and ?1, y is ?0 and <1, x+y is 1, and n is an integer ?5,
(Ar.sup.1).sub.aU(Ar.sup.2).sub.b(Ar.sup.3).sub.c(Ar.sup.4).sub.dII1
(Ar.sup.1).sub.a(Ar.sup.2).sub.bU(Ar.sup.3).sub.c(Ar.sup.4).sub.dII2
(Ar.sup.1).sub.a(Ar.sup.2).sub.b(Ar.sup.3).sub.c(Ar.sup.4).sub.dII3 wherein Ar.sup.1-4 arylene or heteroarylene that has 5 to 20 ring atoms, is mono- or polycyclic, does optionally contain fused rings, is unsubstituted or substituted by one or more identical or different groups L, and is different from formula I, a, b, c, d 0 or 1, wherein in formula II3 a+b+c+d?1 and U is a unit of formula I ##STR00102## wherein R.sup.1 and R.sup.2 have the meanings of H, halogen, CN, straight-chain, branched or cyclic alkyl with 1 to 30, preferably 1 to 20, C atoms, in which one or more CH.sub.2 groups are optionally replaced by O, S, C(?O), C(?S), C(?O)O, OC(?O), NR.sup.0, SiR.sup.0R.sup.00, CF.sub.2, CR.sup.0?CR.sup.00, CY.sup.1?CY.sup.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, and in which one or more CH.sub.2 or CH.sub.3 groups are optionally replaced by a cationic or anionic group, or aryl, heteroaryl, aryloxy or heteroaryloxy, wherein each of the aforementioned cyclic groups has 5 to 20 ring atoms, is mono- or polycyclic, does optionally contain fused rings, and is unsubstituted or substituted by one or more identical or different groups L, where L is F, Cl, CN, NC, NCO, NCS, OCN, SCN, R.sup.0, OR.sup.0, SR.sup.0, C(?O)X.sup.0, C(?O)R.sup.0, C(?O)OR.sup.0, OC(?O)R.sup.0, NH.sub.2, NHR.sup.0, NR.sup.0R.sup.00, C(?O)NHR.sup.0, C(?O)NR.sup.0R.sup.00, SO.sub.3H, SO.sub.2R.sup.0, OH, NO.sub.2, CF.sub.3, SF.sub.5, or optionally substituted silyl, or carbyl or hydrocarbyl with 1 to 20 C atoms that is optionally substituted and optionally comprises one or more hetero atoms Y.sup.1, Y.sup.2 are independently H, F, Cl or CN, X.sup.0 is halogen, and R.sup.0, R.sup.00 are independently H or straight-chain or branched alkyl with 1 to 20 C atoms that is optionally fluorinated, wherein in Formulae III1-III5, R.sup.1 and R.sup.2 have the meanings above, R.sup.3 and R.sup.4 have one of the meanings of R.sup.1, Ar.sup.1, Ar.sup.2, Ar.sup.3, Ar.sup.4, have the meaning above, a, b, c, and d 0 or 1, wherein a+b+c+d?1, and x, y and n have the meanings above, and wherein in formula IV, and R.sup.5 and R.sup.6 have independently of each other one of the meanings F, Cl, CN, NC, NCO, NCS, OCN, SCN, R.sup.0, OR.sup.0, SR.sup.0, C(?O)X.sup.0, C(?O)R.sup.0, C(?O)OR.sup.0, OC(?O)R.sup.0, NH.sub.2, NHR.sup.0, NR.sup.0R.sup.00, C(?O)NHR.sup.0, C(?O)NR.sup.0R.sup.00, SO.sub.3H, SO.sub.2R.sup.0, OH, NO.sub.2, CF.sub.3, SF.sub.5, or optionally substituted silyl, or carbyl or hydrocarbyl with 1 to 20 C atoms that is optionally substituted and optionally comprises one or more hetero atoms X.sup.0 is halogen, R.sup.0, R.sup.00 are independently H or straight-chain or branched alkyl with 1 to 20 C atoms that is optionally fluorinated, or R.sup.5 and R.sup.6 denote, independently of each other, H, F, Br, Cl, I, CH.sub.2Cl, CHO, CR?CR.sub.2, SiRRR, SiRXX, SiRRX, SnRRR, BRR, B(OR)(OR), B(OH).sub.2, OSO.sub.2R, C?CH, C?CSiR.sub.3, ZnX or an endcap group, X and X denote halogen, R, R and R have independently of each other one of the meanings of R.sup.0 and two of R, R and R may also form a cyclosilyl, cyclostannyl, cycloborane or cycloboronate group with 2 to 20 C atoms together with the respective hetero atom to which they are attached.

9. A compound according to claim 5, wherein one or more of Ar.sup.1, Ar.sup.2, Ar.sup.3 and Ar.sup.4 denote arylene or heteroarylene selected from the group consisting of the following formulae ##STR00103## ##STR00104## ##STR00105## ##STR00106## wherein R.sup.11, R.sup.12, R.sup.13, R.sup.14 independently of each other denote H or have one of the meanings of L.

10. A compound according to claim 5, wherein one or more of Ar.sup.1, Ar.sup.2, Ar.sup.3 and Ar.sup.4 denote arylene or heteroarylene selected from the group consisting of the following formulae ##STR00107## ##STR00108## wherein R.sup.11, R.sup.12, R.sup.13, R.sup.14 independently of each other denote H or have one of the meanings of L.

11. A compound according to claim 5, wherein one or more of Ar.sup.1, Ar.sup.2, Ar.sup.3 and Ar.sup.4 denote arylene or heteroarylene selected from the group consisting of the following formulae ##STR00109## ##STR00110## wherein R.sup.11 and R.sup.12 independently of each other denote H or have one of the meanings of L.

12. A compound of formula V1 or V2
R.sup.7(Ar.sup.1).sub.aU(Ar.sup.2).sub.b(Ar.sup.3).sub.c(Ar.sup.4).sub.dR.sup.8 V1
R.sup.7(Ar.sup.1).sub.a(Ar.sup.2).sub.bU(Ar.sup.3).sub.c(Ar.sup.4).sub.dR.sup.8 V2 wherein U is a unit of formula I, ##STR00111## wherein the individual radicals, independently of each other and on each occurrence identically or differently, have the following meanings R.sup.1, R.sup.2 H, halogen, CN, straight-chain, branched or cyclic alkyl with 1 to 30, preferably 1 to 20, C atoms, in which one or more CH.sub.2 groups are optionally replaced by O, S, C(?O), C(?S), C(?O)O, OC(?O), NR.sup.0, SiR.sup.0R.sup.00, CF.sub.2, CR.sup.0?CR.sup.00, CY.sup.1?CY.sup.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, and in which one or more CH.sub.2 or CH.sub.3 groups are optionally replaced by a cationic or anionic group, or aryl, heteroaryl, aryloxy or heteroaryloxy, wherein each of the aforementioned cyclic groups has 5 to 20 ring atoms, is mono- or polycyclic, does optionally contain fused rings, and is unsubstituted or substituted by one or more identical or different groups L, L F, Cl, CN, NC, NCO, NCS, OCN, SCN, R.sup.0, OR.sup.0, SR.sup.0, C(?O)X.sup.0, C(?O)R.sup.0, C(?O)OR.sup.0, OC(?O)R.sup.0, NH.sub.2, NHR.sup.0, NR.sup.0R.sup.00, C(?O)NHR.sup.0, C(?O)NR.sup.0R.sup.00, SO.sub.3H, SO.sub.2R.sup.0, OH, NO.sub.2, CF.sub.3, SF.sub.5, or optionally substituted silyl, or carbyl or hydrocarbyl with 1 to 20 C atoms that is optionally substituted and optionally comprises one or more hetero atoms Y.sup.1, Y.sup.2 H, F, Cl or CN, X.sup.0 halogen, R.sup.0, R.sup.00 H or straight-chain or branched alkyl with 1 to 20 C atoms that is optionally fluorinated, Ar.sup.1-4 arylene or heteroarylene that has 5 to 20 ring atoms, is mono- or polycyclic, does optionally contain fused rings, is unsubstituted or substituted by one or more identical or different groups L, and is different from formula I, a, b, c, d 0 or 1, and R.sup.7 and R.sup.8 are independently of each other selected from the group consisting of H, Cl, Br, I, O-tosylate, O-triflate, O-mesylate, O-nonaflate, SiMe.sub.2F, SiMeF.sub.2, OSO.sub.2Z.sup.1, B(OZ.sup.2).sub.2, CZ.sup.3?C(Z.sup.3).sub.2, C?CH, C?CSi(Z.sup.1).sub.3, ZnX.sup.0 and Sn(Z.sup.4).sub.3, wherein X.sup.0 is halogen, Z.sup.1-4 are selected from the group consisting of C.sub.1-10 alkyl and C.sub.6-12 aryl, each being optionally substituted, and two groups Z.sup.2 may also form a cycloboronate group having 2 to 20 C atoms together with the B- and O-atoms, wherein at least one of R.sup.7 and R.sup.8 is different from H, with the proviso that a+b+c+d?1 or R.sup.7 and/or R.sup.8 are different from Br.

13. A compound of claim 12, which is selected from the following formulae
R.sup.7Ar.sup.1UAr.sup.2R.sup.8 V1a
R.sup.7UR.sup.8 V1b
R.sup.7Ar.sup.1UR.sup.8 V1c
R.sup.7UAr.sup.2R.sup.8 V1d wherein U, Ar.sup.1, Ar.sup.2, R.sup.7 and R.sup.8 are as defined in claim 12.

14. A compound according to claim 5, wherein a) one or more of Ar.sup.1, Ar.sup.2, Ar.sup.3 and Ar.sup.4 denote arylene or heteroarylene selected from the group consisting of the formulae D1, D7, D10, D11, D19, D22, D29, D30, D35, D36, D44, D55, D84, D87, D88, D89, D93, D94, D106, D111, D139, D140 and D141 as defined below, and/or b) one or more of Ar.sup.1, Ar.sup.2, Ar.sup.3 and Ar.sup.4 denote arylene or heteroarylene selected from the group consisting of the formulae A1, A6, A7, A15, A16, A20, A74, A84, A88, A92 and A98 as defined below, and c) one or more of Ar.sup.1, Ar.sup.2, Ar.sup.3 and Ar.sup.4 denote arylene or heteroarylene selected from the group consisting of the formulae Sp1, Sp6, SP10 and Sp13 as defined below, ##STR00112## ##STR00113## ##STR00114## ##STR00115## ##STR00116## ##STR00117## ##STR00118## wherein R.sup.11, R.sup.12, R.sup.13, R.sup.14 independently of each other denote H or have one of the meanings of L.

15. A compound according to claim 1 of formula VI ##STR00119## wherein the individual radicals, independently of each other and on each occurrence identically or differently, have the following meanings Ar.sup.1-8 arylene or heteroarylene that has 5 to 20 ring atoms, is mono- or polycyclic, does optionally contain fused rings, is unsubstituted or substituted by one or more identical or different groups L, and is different from formula I, or CY.sup.1?CY.sup.2, Y.sup.1, Y.sup.2 H, F, Cl or CN, R.sup.1t, 2t H, F, Cl, Br, CN, CF.sub.3, R*, CF.sub.2R*, OR*, SR*, SO.sub.2R*, SO.sub.3R*, C(?O)R*, C(?S)R*, C(?O)CF.sub.2R*, C(?O)OR*, C(?S)OR*, OC(?O)R*, OC(?S)R*, C(?O)SR*, SC(?O)R*, C(?O)NR*R**, NR*C(?O)R*, NHR*, NR*R**, CR*?CR*R**, C?CR*, C?CSiR*R**R***, SiR*R**R***, CH?C(CN)C(?O)OR*, CH?C(COOR*).sub.2, CH?C(CONR*R**).sub.2, CH?C(CN)(Ar.sup.9), ##STR00120## Ar.sup.9,10 aryl or heteroaryl, each having from 4 to 30 ring atoms, optionally containing fused rings and being unsubstituted or substituted with one or more groups L, R*, R**, R*** alkyl with 1 to 20 C atoms which is straight-chain, branched or cyclic, and is unsubstituted, substituted with one or more F or Cl atoms or CN groups, or perfluorinated, and in which one or more C atoms are optionally replaced by O, S, C(O), C(S), SiR.sup.0R.sup.00, NR.sup.0R.sup.00, CHR.sup.0?CR.sup.00 or C?C such that O- and/or S-atoms are not directly linked to each other, R.sup.0, R.sup.00 H or straight-chain or branched alkyl with 1 to 20 C atoms that is optionally fluorinated, a-h 0 or 1, with at least one of a-h being 1, m 1, 2 or 3, with the proviso that m>1 and/or a+b+c+d+e+f+g+h?3 and/or at least one of Ar.sup.1-8 present in the compound is different from ethylenedioxythiophene.

16. A compound of claim 15, wherein Ar.sup.1-10 are selected from the following groups a) the group consisting of the formulae D1, D7, D10, D11, D19, D22, D29, D30, D35, D36, D44, D55, D84, D87, D88, D89, D93, D94, D106, D111, D139, D140 and D141 as defined below, b) the group consisting of the formulae A1, A6, A7, A15, A16, A20, A74, A84, A88, A92 and A98 as defined below, c) the group consisting of the formulae formulae Sp1, Sp6, Sp10 and Sp13 as defined below ##STR00121## ##STR00122## ##STR00123## ##STR00124## ##STR00125## ##STR00126## ##STR00127## wherein R.sup.11, R.sup.12, R.sup.13, R.sup.14 independently of each other denote H or have one of the meanings of L.

17. A mixture comprising one or more compounds according to claim 1 and one or more additional compounds having one or more of semiconducting, charge transport, hole or electron transport, hole or electron blocking, electrically conducting, photoconducting or light emitting properties.

18. A mixture comprising one or more compounds according to claim 1 and one or more n-type organic semiconductors.

19. A mixture of claim 18, wherein the n-type organic semiconductors are selected from fullerenes or substituted fullerenes.

20. A formulation comprising one or more compounds according to claim 1, and further comprising one or more solvents selected from organic solvents.

21. An optical, electrooptical, electronic, electroluminescent or photoluminescent device, or a component thereof, or an assembly comprising it, which is prepared using a formulation according to claim 20.

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

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

24. An optical, electrooptical, electronic, electroluminescent or photoluminescent device, or a component thereof, or an assembly comprising it, which comprises a compound according to claim 1.

25. An optical, electrooptical, electronic, electroluminescent or photoluminescent device of claim 24, which is selected from organic field effect transistors (OFET), organic thin film transistors (OTFT), organic light emitting diodes (OLED), organic light emitting transistors (OLET), organic photovoltaic devices (OPV), organic photodetectors (OPD), organic solar cells, dye-sensitized solar cells (DSSC), perovskite-based solar cells, laser diodes, Schottky diodes, photoconductors and photodetectors.

26. A component of claim 24, which is selected from charge injection layers, charge transport layers, interlayers, planarising layers, antistatic films, polymer electrolyte membranes (PEM), conducting substrates and conducting patterns.

27. An assembly of claim 24, which 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. A bulk heterojunction which comprises, or is being formed from, a mixture according to claim 17.

29. A bulk heterojunction (BHJ) OPV device or inverted BHJ OPV device, comprising a bulk heterojunction of claim 28.

30. A process of preparing a compound according to claim 1, by coupling one or more compounds of formula V1 or V2 with each other and/or with one or more monomers of formulae MI-MIV in an aryl-aryl coupling reaction
R.sup.7(Ar.sup.1).sub.aU(Ar.sup.2).sub.b(Ar.sup.3).sub.c(Ar.sup.4).sub.dR.sup.8 V1
R.sup.7(Ar.sup.1).sub.a(Ar.sup.2).sub.bU(Ar.sup.3).sub.c(Ar.sup.4).sub.dR.sup.8 V2 wherein U is a unit of formula I, ##STR00128## wherein the individual radicals, independently of each other and on each occurrence identically or differently, have the following meanings R.sup.1, R.sup.2 H, halogen, CN, straight-chain, branched or cyclic alkyl with 1 to 30, preferably 1 to 20, C atoms, in which one or more CH.sub.2 groups are optionally replaced by O, S, C(?O), C(?S), C(?O)O, OC(?O), NR.sup.0, SiR.sup.0R.sup.00, CF.sub.2, CR.sup.0?CR.sup.00, CY.sup.1?CY.sup.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, and in which one or more CH.sub.2 or CH.sub.3 groups are optionally replaced by a cationic or anionic group, or aryl, heteroaryl, aryloxy or heteroaryloxy, wherein each of the aforementioned cyclic groups has 5 to 20 ring atoms, is mono- or polycyclic, does optionally contain fused rings, and is unsubstituted or substituted by one or more identical or different groups L, L F, Cl, CN, NC, NCO, NCS, OCN, SCN, R.sup.0, OR.sup.0, SR.sup.0, C(?O)X.sup.0, C(?O)R.sup.0, C(?O)OR.sup.0, OC(?O)R.sup.0, NH.sub.2,NHR.sup.0, NR.sup.0R.sup.00, C(?O)NHR.sup.0, C(?O)NR.sup.0R.sup.00, SO.sub.3H, SO.sub.2R.sup.0, OH, NO.sub.2, CF.sub.3, SF.sub.5, or optionally substituted silyl, or carbyl or hydrocarbyl with 1 to 20 C atoms that is optionally substituted and optionally comprises one or more hetero atoms Y.sup.1, Y.sup.2 H, F, Cl or CN, X.sup.0 halogen, R.sup.0, R.sup.00 H or straight-chain or branched alkyl with 1 to 20 C atoms that is optionally fluorinated, Ar.sup.1-4 arylene or heteroarylene that has 5 to 20 ring atoms, is mono- or polycyclic, does optionally contain fused rings, is unsubstituted or substituted by one or more identical or different groups L, and is different from formula I, a, b, c, d 0 or 1, and R.sup.7 and R.sup.8 are independently of each other H, Cl, Br, I, O-tosylate, O-triflate, O-mesylate, O-nonaflate, SiMe.sub.2F, SiMeF.sub.2, OSO.sub.2Z.sup.1, B(OZ.sup.2).sub.2, CZ.sup.3?C(Z.sup.3).sub.2, C?CH, C?CSi(Z.sup.1).sub.3, ZnX.sup.0 and Sn(Z.sup.4).sub.3, wherein X.sup.0 is halogen, Z.sup.1-4 are selected from the group consisting of C.sub.1-10 alkyl and C.sub.6-12 aryl, each being optionally substituted, and two groups Z.sup.2 may also form a cycloboronate group having 2 to 20 C atoms together with the B- and O-atoms, wherein at least one of R.sup.7 and R.sup.8 is different from H, with the proviso that a+b+c+d?1 or R.sup.7 and/or R.sup.8 are different from Br
R.sup.7Ar.sup.1R.sup.8 MI
R.sup.7Ar.sup.2R.sup.8 MII
R.sup.7Ar.sup.3R.sup.8 MIII
R.sup.7Ar.sup.4R.sup.8 MIV wherein Ar.sup.1-4, R.sup.7 and R.sup.8 have the meanings given above.

Description

DETAILED DESCRIPTION

[0103] The compounds of the present invention are easy to synthesize and exhibit advantageous properties. They show good processability for the device manufacture process, high solubility in organic solvents, and are especially suitable for large scale production using solution processing methods.

[0104] Co-polymers derived from monomers of the present invention and electron donor monomers show low bandgaps, high charge carrier mobilities, high external quantum efficiencies in BHJ solar cells, good morphology when used in p/n-type blends e.g. with fullerenes, high oxidative stability, a long lifetime in electronic devices, and are promising materials for organic electronic OE devices, especially for OPV devices with high power conversion efficiency.

[0105] The compounds of the present invention are especially suitable as p-type semiconductors for the preparation of blends of p-type and n-type semiconductors which are suitable for use in BHJ photovoltaic devices.

[0106] Besides, the compounds of the present invention show the following advantageous properties: [0107] i) Additional solubility can be introduced into the compound by inclusion of various solubilizing groups in R.sup.1 and R.sup.2 positions. [0108] ii) Additional fine-tuning of the electronic energies (HOMO/LUMO levels) by co-polymerisation with appropriate co-monomer(s) can afford attractive candidate materials for OPV applications. [0109] iii) The BBT units have planar structures that enable strong pi-pi stacking in the solid state leading to improved charge transport properties in the form of higher charge carrier mobility. [0110] iv) An incorporation of various R.sup.1 and R.sup.2 substituents into the BBT core results in monomers with either electron donating property, like for example dialkyl-BBT, or electron accepting property, like for example dialkyl ester-BBT. [0111] v) The BBT unit can thus be altered from a donor unit to an acceptor unit by switching the nature of the solubilising groups, for example from electron donating groups like alkyl or alkoxy to electron withdrawing groups like ketone or ester, thus allowing a much broader applicability of the core for use in OPV or OPD polymers [0112] vi) Using both BBT units substituted by electron donating groups like alkyl or alkoxy and BBT units substituted by to electron withdrawing groups like ketone or ester, it is possible to create a donor-acceptor polymer from BBT units, optionally with spacer units like thiophene, dithiophene or thienothiophene to keep the backbone flat, but without further donor or acceptor units. Such polymers are expected to have a high Voc.

[0113] Preferably R.sup.1 and R.sup.2 in the units of formula I are different from H.

[0114] Preferably R.sup.1 and R.sup.2 in the units of formula I are selected from the following groups or any combination thereof: [0115] the group consisting of R, OR and SR wherein R is straight-chain or branched alkyl with 1 to 20 C atoms which is unsubstituted or substituted by one or more F atoms, [0116] the group consisting of C(?O)R, C(?O)OR, OC(?O)R, C(?O)NHR and C(?O)NRR.sup.n, wherein R and R.sup.n are independently of each other straight-chain or branched alkyl with 1 to 20 C atoms that is optionally fluorinated, [0117] the group consisting of aryl, aryloxy, heteroaryl and heteroaryloxy, each of which has 4 to 20 ring atoms and optionally contains fused rings and is unsubstituted or substituted by one or more groups L as defined in formula I.

[0118] Very preferably R.sup.1 and R.sup.2 in the units of formula I denote R or C(?O)OR, wherein R is straight-chain or branched alkyl with 1 to 20 C atoms that is optionally fluorinated.

[0119] If R.sup.1 or R.sup.2 denote an aryl(oxy) or heteroaryl(oxy) group, it is preferably selected from phenyl, pyrrole, furan, pyridine, thiazole, thiophene, thieno[3,2-b]thiophene or thieno[2,3-b]thiophene, each of which is unsubstituted or substituted with F or alkyl, alkoxy or thioalkyl each having from 1 to 20 C atoms and being optionally fluorinated.

[0120] In another preferred embodiment of the present invention, R.sup.1 and/or R.sup.2 denote straight-chain, branched or cyclic alkyl with 1 to 20 C-atoms wherein one or more CH.sub.2 or CH.sub.3 groups are substituted by a cationic or anionic group.

[0121] The cationic group is preferably selected from the group consisting of phosphonium, sulfonium, ammonium, uronium, thiouronium, guanidinium or heterocyclic cations such as imidazolium, pyridinium, pyrrolidinium, triazolium, morpholinium or piperidinium cation.

[0122] Preferred cationic groups are selected from the group consisting of tetraalkylammonium, tetraalkylphosphonium, N-alkylpyridinium, N,N-dialkylpyrrolidinium, 1,3-dialkylimidazolium, wherein alkyl preferably denotes a straight-chain or branched alkyl group with 1 to 12 C atoms.

[0123] Further preferred cationic groups are selected from the group consisting of the following formulae

##STR00006## ##STR00007## ##STR00008##

[0124] wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.4 denote, independently of each other, H, a straight-chain or branched alkyl group with 1 to 12 C atoms or non-aromatic carbo- or heterocyclic group or an aryl or heteroaryl group, each of the aforementioned groups having 3 to 20, preferably 5 to 15, ring atoms, being mono- or polycyclic, and optionally being substituted by one or more identical or different substituents L as defined below, or denote a link to the respective group R.sup.1-4.

[0125] In the above cationic groups of the above-mentioned formulae any one of the groups R.sup.1, R.sup.2, R.sup.3 and R.sup.4 (if they replace a CH.sub.3 group) can denote a link to the group R.sup.1, or two neighbored groups R.sup.1, R.sup.2, R.sup.3 or R.sup.4 (if they replace a CH.sub.2 group) can denote a link to the respective group R.sup.1-4.

[0126] The anionic group is preferably selected from the group consisting of borate, imide, phosphate, sulfonate, sulfate, succinate, naphthenate or carboxylate, very preferably from phosphate, sulfonate or carboxylate.

[0127] The compounds according to the present invention include small molecules, monomers, oligomers and polymers.

[0128] A preferred embodiment of the present invention relates to a conjugated polymer comprising, preferably consisting of, one or more repeating units of formula II1 or II2, and optionally one or more repeating units of formula II3:

(Ar.sup.1).sub.aU(Ar.sup.2).sub.b(Ar.sup.3).sub.c(Ar.sup.4).sub.dII1

(Ar.sup.1).sub.a(Ar.sup.2).sub.bU(Ar.sup.3).sub.c(Ar.sup.4).sub.dII2

(Ar.sup.1).sub.a(Ar.sup.2).sub.b(Ar.sup.3).sub.c(Ar.sup.4).sub.dII3

[0129] wherein the individual radicals, independently of each other and on each occurrence identically or differently, have the following meanings [0130] U a unit of formula I as defined above and below, [0131] Ar.sup.1-4 arylene or heteroarylene that has 5 to 20 ring atoms, is mono- or polycyclic, does optionally contain fused rings, is unsubstituted or substituted by one or more identical or different groups L, and is different from formula I, [0132] a, b, c, d 0 or 1, wherein in formula II3 a+b+c+d?1.

[0133] Preferably the conjugated polymer comprises one or more repeating units of formula II1 or II2 wherein a+b+c+d?1.

[0134] Further preferably the conjugated polymer comprises one or more repeating units of formula II1 wherein b=1 and a=c=d=0 and one or more repeating units of formula II3 wherein a=b=1 and c=d=0.

[0135] Further preferably the conjugated polymer comprises two or more distinct repeating units of formula II1 wherein b=1 and a=c=d=0.

[0136] Further preferably at least one of Ar.sup.1, Ar.sup.2, Ar.sup.3 and Ar.sup.4 is an arylene or heteroarylene group as being defined in formula II1 and having electron donor property.

[0137] Preferably L denotes F or is selected from the following groups [0138] the group consisting of R, OR and SR wherein R is straight-chain or branched alkyl with 1 to 20 C atoms which is unsubstituted or substituted by one or more F atoms, [0139] the group consisting of C(?O)R, C(?O)OR, OC(?O)R, C(?O)NHR and C(?O)NRR.sup.n, wherein R and R.sup.n are independently of each other straight-chain or branched alkyl with 1 to 20 C atoms that is optionally fluorinated,

[0140] Further preferably the conjugated polymer according to the present invention is selected of formula III:

*?(A).sub.x-(B).sub.y?.sub.n* III

[0141] wherein

[0142] A is a unit of formula I, II1 or II2 as defined above and below,

[0143] B is a unit of formula I, II1, II2 or II3 as defined above and below,

[0144] x is >0 and ?1,

[0145] y is ?0 and <1,

[0146] x+y is 1, and

[0147] n is an integer ?5.

[0148] Preferred polymers of formula III are selected from the following formulae

##STR00009##

[0149] wherein

[0150] R.sup.1 and R.sup.2 have the meanings of formula I or one of the preferred meanings given above and below,

[0151] R.sup.3 and R.sup.4 have one of the meanings of R.sup.1 or its preferred meanings given above and below,

[0152] Ar.sup.1, Ar.sup.2, Ar.sup.3, Ar.sup.4, a, b, c and d have the meanings of formula II1 or one of the preferred meanings given above and below,

[0153] x, y and n have the meanings of formula III or one of the preferred meanings given above and below, and

[0154] preferably Ar.sup.3 is selected from arylene or heteroarylene units as described above and below having electron donor properties, and

[0155] preferably at least one of the meanings of R.sup.1 and R.sup.2 is different from at least one of the meanings of R.sup.3 and R.sup.4.

[0156] In the polymers of formula III and III1-III5, x and y denote the mole fraction of repeating units A and B, respectively, and n denotes the degree of polymerisation or total number of repeating units A and B. These formulae include block copolymers, random or statistical copolymers and alternating copolymers of A and B, as well as homopolymers of A for the case when x>0 and y=0.

[0157] In the polymers of formula III and III1-III5, x is preferably from 0.1 to 0.9, very preferably from 0.3 to 0.7.

[0158] In the polymers of formula III and III1-III5, y is preferably from 0.1 to 0.9, very preferably from 0.3 to 0.7.

[0159] In the polymers according to the present invention, the total number of repeating units n is preferably from 2 to 10,000. The total number of repeating units n is preferably ?5, very preferably ?10, most preferably ?50, and preferably ?500, very preferably ?1,000, most preferably ?2,000, including any combination of the aforementioned lower and upper limits of n.

[0160] The polymers of the present invention include homopolymers and copolymers, like statistical or random copolymers, alternating copolymers and block copolymers, as well as combinations thereof.

[0161] Further preferably the conjugated polymer is selected of formula IV

R.sup.5-chain-R.sup.6 IV

[0162] wherein chain denotes a polymer chain selected of formulae III and III1-III5, and R.sup.5 and R.sup.6 have independently of each other one of the meanings of L as defined above, or denote, independently of each other, H, F, Br, Cl, I, CH.sub.2Cl, CHO, CR?CR.sub.2, SiRRR, SiRXX, SiRRX, SnRRR, BRR, B(OR)(OR), B(OH).sub.2, OSO.sub.2R, C?CH, C?CSiR.sub.3, ZnX or an endcap group, X and X denote halogen, R, R and R have independently of each other one of the meanings of R.sup.0 given in formula I, and preferably denote alkyl with 1 to 12 C atoms, and two of R, R and R may also form a cyclosilyl, cyclostannyl, cycloborane or cycloboronate group with 2 to 20 C atoms together with the respective hetero atom to which they are attached.

[0163] Preferred endcap groups R.sup.5 and R.sup.6 are H, C.sub.1-20 alkyl, or optionally substituted C.sub.6-12 aryl or C.sub.2-10 heteroaryl, very preferably H or phenyl.

[0164] A further preferred embodiment of the present invention relates to a monomer of formula V1 or V2

R.sup.7(Ar.sup.1).sub.aU(Ar.sup.2).sub.b(Ar.sup.3).sub.c(Ar.sup.4).sub.dR.sup.8 V1

R.sup.7(Ar.sup.1).sub.a(Ar.sup.2).sub.bU(Ar.sup.3).sub.c(Ar.sup.4).sub.dR.sup.8 V2

[0165] wherein U, Ar.sup.1-4, a, b, c and d have the meanings of formula II1, or one of the preferred meanings as described above and below, and R.sup.7 and R.sup.8 are independently of each other selected from the group consisting of H, which is preferably an activated CH bond, Cl, Br, I, O-tosylate, O-triflate, O-mesylate, O-nonaflate, SiMe.sub.2F, SiMeF.sub.2, OSO.sub.2Z.sup.1, B(OZ.sup.2).sub.2, CZ.sup.3?C(Z.sup.3).sub.2, C?CH, C?CSi(Z.sup.1).sub.3, ZnX.sup.0 and Sn(Z.sup.4).sub.3, wherein X.sup.0 is halogen, Z.sup.1-4 are selected from the group consisting of alkyl and aryl, preferably C.sub.1-10 alkyl and C.sub.6-12 aryl, each being optionally substituted, and two groups Z.sup.2 may also form a cycloboronate group having 2 to 20 C atoms together with the B- and O-atoms, and wherein at least one of R.sup.7 and R.sup.8 is different from H, and preferably both of R.sup.1 and R.sup.2 are different from H,

[0166] with the proviso that a+b+c+d?1 or R.sup.7 and/or R.sup.8 are different from Br, preferably different from halogen.

[0167] Very preferred are monomers of formula V1 and V2 and their subformulae wherein a+b+c+d?1.

[0168] Further preferred are monomers of formula V1 and its subformulae wherein a+b+c+d=0.

[0169] Further preferred are monomers of formula V1 and V2 and their subformulae wherein R.sup.7 and R.sup.8 are selected from B(OZ.sup.2).sub.2 and Sn(Z.sup.4).sub.3.

[0170] Further preferred are monomers selected from the following formulae

R.sup.7Ar.sup.1UAr.sup.2R.sup.8 V1a

R.sup.7UR.sup.8 V1b

R.sup.7Ar.sup.1UR.sup.8 V1c

R.sup.7UAr.sup.2R.sup.8 V1d

[0171] wherein U, Ar.sup.1, Ar.sup.2, R.sup.7 and R.sup.8 are as defined in formula V1.

[0172] Very preferred are monomers of formula V1 and V2 and their subformulae wherein R.sup.7 and R.sup.8 are selected from Br, B(OZ.sup.2).sub.2 and Sn(Z.sup.4).sub.3.

[0173] A further preferred embodiment of the present invention relates to a small molecule or oligomer of formula VI

##STR00010##

[0174] wherein the individual radicals, independently of each other and on each occurrence identically or differently, have the following meanings [0175] Ar.sup.1-8 one of the meanings given for Ar.sup.1 in formula II1 or one of its preferred meanings given above and below, or a unit of formula I as defined above and below, or CY.sup.1?CY.sup.2, [0176] Y.sup.1, Y.sup.2 H, F, Cl or CN, [0177] R.sup.1t, 2t H, F, Cl, Br, CN, CF.sub.3, R*, CF.sub.2R*, OR*, SR*, SO.sub.2R*, SO.sub.3R*, C(?O)R*, C(?S)R*, C(?O)CF.sub.2R*, C(?O)OR*, C(?S)OR*, OC(?O)R*, OC(?S)R*, C(?O)SR*, SC(?O)R*, C(?O)NR*R**, NR*C(?O)R*, NHR*, NR*R**, CR*?CR*R**, C?CR*, C?CSiR*R**R***, SiR*R**R***, CH?C(CN)C(?O)OR*, CH?C(COOR*).sub.2, CH?C(CONR*R**).sub.2, CH?C(CN)(Ar.sup.9),

##STR00011## [0178] Ar.sup.9,10 aryl or heteroaryl, each having from 4 to 30 ring atoms, optionally containing fused rings and being unsubstituted or substituted with one or more groups L as defined in formula I, [0179] R*, R**, R*** alkyl with 1 to 20 C atoms which is straight-chain, branched or cyclic, and is unsubstituted, or substituted with one or more F or Cl atoms or CN groups, or perfluorinated, and in which one or more C atoms are optionally replaced by O, S, C(O), C(S), SiR.sup.0R.sup.00, NR.sup.0R.sup.00, CHR.sup.0?CR.sup.00 or C?C such that O- and/or S-atoms are not directly linked to each other, [0180] R.sup.0, R.sup.00 H or or straight-chain or branched alkyl with 1 to 20, preferably 1 to 12 C atoms that is optionally fluorinated, [0181] a-h 0 or 1, preferably with at least one of a-h being 1, [0182] m 1, 2 or 3,

[0183] with the proviso that m>1 and/or a+b+c+d+e+f+g+h?3 and/or at least one of Ar.sup.1-8 present in the compound is different from ethylenedioxythiophene (formula D18).

[0184] Especially preferred are repeating units, monomers, oligomers, polymers and small molecules of formulae II1, II2, III, III1-III5, IV, V1, V2, V1a-V1d, VI and their subformulae wherein one or more of Ar.sup.1, Ar.sup.2, Ar.sup.3 and Ar.sup.4 denote arylene or heteroarylene, preferably having electron donor properties, selected from the group consisting of the following formulae

##STR00012## ##STR00013## ##STR00014## ##STR00015## ##STR00016## ##STR00017## ##STR00018## ##STR00019## ##STR00020## ##STR00021## ##STR00022## ##STR00023## ##STR00024## ##STR00025## ##STR00026## ##STR00027## ##STR00028## ##STR00029## ##STR00030## ##STR00031##

[0185] wherein R.sup.11, R.sup.12, R.sup.13, R.sup.14, R.sup.15, R.sup.16, R.sup.17 and R.sup.18 independently of each other denote H or have one of the meanings of L as defined above and below.

[0186] Preferred donor units are selected from formulae D1, D7, D10, D11, D19, D22, D29, D30, D35, D36, D44, D55, D84, D87, D88, D89, D93, D94, D106, D111, D139, D140 or D141 wherein preferably at least one of R.sup.11, R.sup.12, R.sup.13 and R.sup.14 is different from H.

[0187] Further preferred are repeating units, monomers, oligomers, polymers and small molecules of formulae II1, II2, III, III1-III5, IV, V1, V2, V1a-V1d, VI and their subformulae wherein one or more of Ar.sup.1, Ar.sup.2, Ar.sup.3 and Ar.sup.4 denote arylene or heteroarylene, preferably having electron acceptor properties, selected from the group consisting of the following formulae

##STR00032## ##STR00033## ##STR00034## ##STR00035## ##STR00036## ##STR00037## ##STR00038## ##STR00039## ##STR00040## ##STR00041## ##STR00042## ##STR00043## ##STR00044## ##STR00045## ##STR00046## ##STR00047## ##STR00048## ##STR00049## ##STR00050##

[0188] wherein R.sup.11, R.sup.12, R.sup.13, R.sup.14, R.sup.15 and R.sup.16 independently of each other denote H or have one of the meanings of L as defined above and below.

[0189] Preferred acceptor units are selected from formulae A1, A6, A7, A15, A16, A20, A74, A84, A88, A92 or A98 wherein preferably at least one of R.sup.11, R.sup.12, R.sup.13 and R.sup.14 is different from H.

[0190] Further preferred are repeating units, monomers, oligomers, polymers and small molecules of formulae II1, II2, III, III1-III5, IV, V1, V2, V1a-V1d, VI and their subformulae wherein one or more of Ar.sup.1, Ar.sup.2, Ar.sup.3 and Ar.sup.4 denote arylene or heteroarylene selected from the group consisting of the following formulae

##STR00051## ##STR00052##

[0191] wherein R.sup.11 and R.sup.12 independently of each other denote H or have one of the meanings of L as defined above and below.

[0192] Very preferred are units selected from formulae Sp1, Sp6, Sp10, Sp13, wherein preferably one of R.sup.11 and R.sup.12 is H or both R.sup.11 and R.sup.12 are H.

[0193] Further preferred are repeating units, monomers and polymers of formulae II1, II2, III, III1-III5, IV, V1, V2, V1a-V1d and their subformulae wherein [0194] a) one or more of Ar.sup.1, Ar.sup.2, Ar.sup.3 and Ar.sup.4 denote arylene or heteroarylene, preferably having electron donor properties, selected from the group consisting of the formulae D1-D145, very preferably of the formulae D1, D7, D10, D11, D19, D22, D29, D30, D35, D36, D44, D55, D84, D87, D88, D89, D93, D94, D106, D111, D139, D140 and D141, and/or [0195] b) one or more of Ar.sup.1, Ar.sup.2, Ar.sup.3 and Ar.sup.4 denote arylene or heteroarylene, preferably having electron acceptor properties, selected from the group consisting of the formulae A1-A98, very preferably of the formulae A1, A6, A7, A15, A16, A20, A74, A84, A88, A92 and A98, and [0196] c) one or more of Ar.sup.1, Ar.sup.2, Ar.sup.3 and Ar.sup.4 denote arylene or heteroarylene selected from the group consisting of the formulae Sp1-Sp15, very preferably of the formulae Sp1, Sp6, Sp10 and Sp13.

[0197] Further preferred are polymers of formula III3 and III5 wherein Ar.sup.1 and Ar.sup.2 have the same meaning and are selected from formulae D1, D7, D10, D11, D19, D22, D29, D30, D35, D36, D44, D55, D84, D87, D88, D89, D93, D94, D106, D111, D139, D140 and D141, and R.sup.1 and R.sup.2 denote R or OR, and R.sup.3 and R.sup.4 denote C(?O)R or C(?O)OR with R being as defined above.

[0198] Further preferred are oligomers and small molecules of formula VI wherein Ar.sup.1-10 are selected from the following groups [0199] a) the group consisting of the formulae D1-D145, very preferably of the formulae D1, D7, D10, D11, D19, D22, D29, D30, D35, D36, D44, D55, D84, D87, D88, D89, D93, D94, D106, D111, D139, D140 and D141, [0200] b) the group consisting of the formulae A1-A98, very preferably of the formulae A1, A6, A7, A15, A16, A20, A74, A84, A88, A92 or A98, [0201] c) the group consisting of the formulae Sp1-Sp15, very preferably of the formulae Sp1, Sp6, Sp10 and Sp13.

[0202] The polymers according to the present invention can be prepared for example by copolymerising one or more monomers of formula V1, V2 or V1a-V1d with each other or with one or monomers of the following formulae in an aryl-aryl coupling reaction

R.sup.7Ar.sup.1R.sup.8 MI

R.sup.7Ar.sup.2R.sup.8 MII

R.sup.7Ar.sup.3R.sup.8 MIII

R.sup.7Ar.sup.4R.sup.8 MIV

[0203] wherein Ar.sup.1-4, R.sup.7 and R.sup.8 have the meanings given in formula II2 and V1 or one of the preferred meanings given above and below.

[0204] The polymer according to the present invention can be synthesized according to or in analogy to methods that are known to the skilled person and are described in the literature. Other methods of preparation can be taken from the examples.

[0205] For example, the polymer can be suitably prepared by aryl-aryl coupling reactions, such as Yamamoto coupling, CH activation coupling, Suzuki coupling, Stille coupling, Sonogashira coupling, Heck coupling or Buchwald coupling. Suzuki coupling, Stille coupling and Yamamoto coupling are especially preferred. The monomers which are polymerised to form the repeat units of the polymers can be prepared according to methods which are known to the person skilled in the art.

[0206] Preferably the polymer is prepared from monomers selected from formulae V1, V2, V1a-d and MI-MIV as described above.

[0207] Another aspect of the invention is a process for preparing a polymer by coupling one or more identical or different monomers selected from formulae V1, V2, V1a-d with each other and/or with one or more co-monomers, preferably selected from formulae MI-MIV, in a polymerisation reaction, preferably in an aryl-aryl coupling reaction.

[0208] Preferred aryl-aryl coupling and polymerisation methods used in the processes described above and below are Yamamoto coupling, Kumada coupling, Negishi coupling, Suzuki coupling, Stille coupling, Sonogashira coupling, Heck coupling, CH activation coupling, Ullmann coupling or Buchwald coupling. Especially preferred are Suzuki coupling, Negishi coupling, Stille coupling and Yamamoto coupling. Suzuki coupling is described for example in WO 00/53656 A1. Negishi coupling is described for example in J. Chem. Soc., Chem. Commun., 1977, 683-684. Yamamoto coupling is described in for example in T. Yamamoto et al., Prog. Polym. Sci., 1993, 17, 1153-1205, or WO 2004/022626 A1. Stille coupling is described for example in Z. Bao et al., J. Am. Chem. Soc., 1995, 117, 12426-12435. CH activation is described for example for example in M. Leclerc et al, Angew. Chem. Int. Ed. 2012, 51, 2068-2071. For example, when using Yamamoto coupling, monomers having two reactive halide groups are preferably used. When using Suzuki coupling, monomers having two reactive boronic acid or boronic acid ester groups or two reactive halide groups are preferably used. When using Stille coupling, monomers having two reactive stannane groups or two reactive halide groups are preferably used. When using Negishi coupling, monomers having two reactive organozinc groups or two reactive halide groups are preferably used. When synthesizing a linear polymer by CH activation polymerisation, preferably a monomer as described above is used wherein at least one reactive group is an activated hydrogen bond.

[0209] Preferred catalysts, especially for Suzuki, Negishi or Stille coupling, are selected from Pd(0) complexes or Pd(II) salts. Preferred Pd(0) complexes are those bearing at least one phosphine ligand such as Pd(Ph.sub.3P).sub.4. Another preferred phosphine ligand is tris(ortho-tolyl)phosphine, i.e. Pd(o-Tol.sub.3P).sub.4. Preferred Pd(II) salts include palladium acetate, i.e. Pd(Oac).sub.2 or trans-di(?-acetato)-bis[o-(di-o-tolylphosphino)benzyl]dipalladium(II). Alternatively the Pd(0) complex can be prepared by mixing a Pd(0) dibenzylideneacetone complex, for example tris(dibenzyl-ideneacetone)dipalladium(0), bis(dibenzylideneacetone)palladium(0), or Pd(II) salts e.g. palladium acetate, with a phosphine ligand, for example triphenylphosphine, tris(ortho-tolyl)phosphine, tris(o-methoxyphenyl)phosphine or tri(tert-butyl)phosphine. Suzuki polymerisation is performed in the presence of a base, for example sodium carbonate, potassium carbonate, cesium carbonated, lithium hydroxide, potassium phosphate or an organic base such as tetraethylammonium carbonate or tetraethylammonium hydroxide. Yamamoto polymerisation employs a Ni(0) complex, for example bis(1,5-cyclooctadienyl) nickel(0).

[0210] Suzuki, Stille or CH activation coupling polymerisation may be used to prepare homopolymers as well as statistical, alternating and block random copolymers. Statistical, random block copolymers or block copolymers can be prepared for example from the above monomers, wherein one of the reactive groups is halogen and the other reactive group is a CH activated bond, boronic acid, boronic acid derivative group or and alkylstannane. The synthesis of statistical, alternating and block copolymers is described in detail for example in WO 03/048225 A2 or WO 2005/014688 A2.

[0211] As alternatives to halogen as described above, leaving groups of formula OSO.sub.2Z.sup.1 can be used wherein Z.sup.1 is as defined above. Particular examples of such leaving groups are tosylate, mesylate and triflate.

[0212] Preferred polymerisation conditions lead to alternating polymers which are particularly preferred for OTFT application, whereas statistical block co-polymers are prepared preferably for OPV and OPD application. Preferred polycondensation are Suzuki coupling, Stille coupling, Sonogashira coupling, Heck coupling or Buchwald coupling, Negishi coupling or CH activation coupling where the first set of reactive groups is composed of Cl, Br, I, O-tosylate, O-triflate, O-mesylate and O-nonaflate and the second set of reactive groups is composed of H, SiR.sub.2F, SiRF.sub.2, B(OR).sub.2, CR?CHR, C?CH, ZnX, MgX and Sn(R.sub.3). If a Yamamoto coupling reaction is used to prepare the polymer, the reactive monomer ends are both composed independently of Cl, Br, I, O-tosylate, O-triflate, O-mesylate and O-nonaflate.

[0213] Suitable and preferred methods for preparing compounds according to the present invention are illustrated in the reaction schemes below.

[0214] Schemes 1-4 show the synthesis of the units of formula I. Therein R and R have one of the meanings of R.sup.1 given in formula I, for example alkyl, X.sup.1,2 are Br, SnR.sub.3 or B(OR).sub.2, Ar.sup.1,4 are arylene or heteroarylene as defined for example in formula II1.

[0215] Synthesis of the 4,8-benzo[1,2-d;4,5-d]bisthiazole core can be achieved as shown by Malika Jeffries-E L in J. Org. Chem., 2010, 75 (2), 495-497, as exemplarily illustrated in Scheme 1.

##STR00053##

[0216] An alternative synthesis was published by Persephonis et al., Org. Lett., 2014, 16 (24), 6358-6361, as shown in Scheme 2.

##STR00054##

[0217] Synthesis of the alky-functionalised core can be achieved as shown in Scheme 3.

##STR00055##

[0218] Synthesis of the ester-functionalised core can be achieved as shown in Scheme 4.

##STR00056##

[0219] The synthesis of alternating co-polymers of the 4,8-benzo[1,2-d;4,5-d]bisthiazole core is shown in Scheme 5. Therein X1=Br and X2=SnR.sub.3 or X1=Br and X2=B(OR).sub.2 or X1=SnR.sub.3 and X2=Br or X1=B(OR).sub.2 and X2=Br or X1=Br or Cl, Ar.sub.x is optionally substituted arylene or heteroarylene as defined in formula II1, and a-d are 0 or 1 with a+b+c+d?0, and R is for example alkyl.

##STR00057## ##STR00058##

[0220] The synthesis of statistical block co-polymers of the 4,8-benzo[1,2-d;4,5-d]bisthiazole core is shown in Scheme 6, wherein the individual radicals are as defined in Scheme 5.

##STR00059##

[0221] The synthesis of oliogomers and small molecules based on the 4,8-benzo[1,2-d;4,5-d]bisthiazole core is shown in Scheme 7.

[0222] Alternatively these compounds can be obtained via a convergent synthesis strategy as shown in Scheme 8. Therein X1=Br and X2=SnR.sub.3 or B(OR).sub.2 or X1=SnR.sub.3 and X2=Br or X1=B(OR).sub.2 and X2=Br, Ar.sub.1-8 correspond to Ar.sup.1-8 as defined in formula VI, and Ar.sub.5Ar.sub.6Ar.sub.7Ar.sub.8R.sup.2.sub.end is identical to Ar.sub.4Ar.sub.3Ar.sub.2Ar.sub.1R.sup.1.sub.end, and R.sup.1.sub.end and R.sup.2.sub.end correspond to R.sup.1t and R.sup.2t in formula VI.

##STR00060##

##STR00061##

[0223] Alternatively the asymmetric small molecules based on 4,8-benzo[1,2-d;4,5-d]bisthiazole obtained via a convergent synthesis strategy as shown in Scheme 9, wherein the individual radicals are as defined in Scheme 7.

##STR00062##

[0224] The synthesis of asymmetric compounds containing multiple 4,8-benzo[1,2-d;4,5-d]bisthiazole units via a convergent synthesis strategy is shown in Scheme 10, wherein the individual radicals are as defined in Scheme 7, and 1<n?3.

##STR00063##

[0225] Further substitution can be added to the 4,8-benzo[1,2-d;4,5-d]bisthiazole core at the R.sup.x.sub.end substitution after the 4,8-benzo[1,2-d;4,5-d]bisthiazole core organic semiconductors have been prepared as shown in Scheme 11, wherein the individual radicals are as defined in Scheme 10.

##STR00064##

[0226] The novel methods of preparing a compound, monomer or polymer as described above and below, and the novel monomers and intermediates used therein, are further aspects of the invention.

[0227] The polymer according to the present invention can also be used in mixtures or polymer blends, for example together with monomeric compounds or together with other polymers having charge-transport, semiconducting, electrically conducting, photoconducting and/or light-emitting semiconducting properties, or for example with polymers having hole blocking, electron blocking properties for use as interlayers, charge blocking layers, charge transporting layer in OLED devices, OPV devices or perovskite based solar cells. Thus, another aspect of the invention relates to a polymer blend comprising one or more polymers according to the present invention and one or more further polymers having one or more of the above-mentioned properties. These blends can be prepared by conventional methods that are described in prior art and known to the skilled person. Typically the polymers are mixed with each other or dissolved in suitable solvents and the solutions combined.

[0228] Another aspect of the invention relates to a formulation comprising one or more polymers, polymer blends or mixtures as described above and below and one or more organic solvents.

[0229] Preferred solvents are aliphatic hydrocarbons, chlorinated hydrocarbons, aromatic hydrocarbons, ketones, ethers and mixtures thereof. Additional solvents which can be used include 1,2,4-trimethylbenzene, 1,2,3,4-tetra-methyl benzene, pentylbenzene, mesitylene, cumene, cymene, cyclohexylbenzene, diethylbenzene, tetralin, decalin, 2,6-lutidine, 2-fluoro-m-xylene, 3-fluoro-o-xylene, 2-chlorobenzotrifluoride, N,N-dimethylformamide, 2-chloro-6-fluorotoluene, 2-fluoroanisole, anisole, 2,3-dimethylpyrazine, 4-fluoroanisole, 3-fluoroanisole, 3-trifluoro-methylanisole, 2-methylanisole, phenetol, 4-methylanisole, 3-methylanisole, 4-fluoro-3-methylanisole, 2-fluorobenzonitrile, 4-fluoroveratrol, 2,6-dimethylanisole, 3-fluorobenzo-nitrile, 2,5-dimethylanisole, 2,4-dimethylanisole, benzonitrile, 3,5-dimethyl-anisole, N,N-dimethylaniline, ethyl benzoate, 1-fluoro-3,5-dimethoxy-benzene, 1-methylnaphthalene, N-methylpyrrolidinone, 3-fluorobenzo-trifluoride, benzotrifluoride, dioxane, trifluoromethoxy-benzene, 4-fluorobenzotrifluoride, 3-fluoropyridine, toluene, 2-fluoro-toluene, 2-fluorobenzotrifluoride, 3-fluorotoluene, 4-isopropylbiphenyl, phenyl ether, pyridine, 4-fluorotoluene, 2,5-difluorotoluene, 1-chloro-2,4-difluorobenzene, 2-fluoropyridine, 3-chlorofluoro-benzene, 1-chloro-2,5-difluorobenzene, 4-chlorofluorobenzene, chloro-benzene, o-dichlorobenzene, 2-chlorofluorobenzene, p-xylene, m-xylene, o-xylene or mixture of o-, m-, and p-isomers. Solvents with relatively low polarity are generally preferred. For inkjet printing solvents and solvent mixtures with high boiling temperatures are preferred. For spin coating alkylated benzenes like xylene and toluene are preferred.

[0230] Examples of especially preferred solvents include, without limitation, dichloromethane, trichloromethane, tetrachloromethane, chlorobenzene, o-dichlorobenzene, 1,2,4-trichlorobenzene, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, 1,8-diiodooctane, 1-chloronaphthalene, 1,8-octane-dithiol, anisole, 2,5-di-methylanisole, 2,4-dimethylanisole, toluene, o-xylene, m-xylene, p-xylene, mixture of o-, m-, and p-xylene isomers, 1,2,4-trimethylbenzene, mesitylene, cyclohexane, 1-methylnaphthalene, 2-methylnaphthalene, 1,2-dimethylnaphthalene, tetraline, decaline, indane, 1-methyl-4-(1-methylethenyl)-cyclohexene (d-Limonene), 6,6-dimethyl-2-methylenebicyclo[3.1.1]heptanes (?-pinene), methyl benzoate, ethyl benzoate, nitrobenzene, benzaldehyde, tetrahydrofuran, 1,4-dioxane, 1,3-dioxane, morpholine, acetone, methylethylketone, ethyl acetate, n-butyl acetate, N,N-dimethylformamide, dimethylacetamide, dimethylsulfoxide and/or mixtures thereof.

[0231] The concentration of the polymers in the solution is preferably 0.1 to 10% by weight, more preferably 0.5 to 5% by weight. Optionally, the solution also comprises one or more binders to adjust the rheological properties, as described for example in WO 2005/055248 A1.

[0232] After the appropriate mixing and ageing, solutions are evaluated as one of the following categories: complete solution, borderline solution or insoluble. The contour line is drawn to outline the solubility parameter-hydrogen bonding limits dividing solubility and insolubility. Complete solvents falling within the solubility area can be chosen from literature values such as published in Crowley, J. D., Teague, G. S. Jr and Lowe, J. W. Jr., Journal of Paint Technology, 1966, 38 (496), 296. Solvent blends may also be used and can be identified as described in Solvents, W. H. Ellis, Federation of Societies for Coatings Technology, p 9-10, 1986.

[0233] Such a procedure may lead to a blend of non solvents that will dissolve both the polymers of the present invention, although it is desirable to have at least one true solvent in a blend.

[0234] The polymer according to the present invention can also be used in patterned OSC layers in the devices as described above and below. For applications in modern microelectronics it is generally desirable to generate small structures or patterns to reduce cost (more devices/unit area), and power consumption. Patterning of thin layers comprising a polymer according to the present invention can be carried out for example by photolithography, electron beam lithography or laser patterning.

[0235] For use as thin layers in electronic or electrooptical devices the polymers, polymer blends or formulations of the present invention may be deposited by any suitable method. Liquid coating of devices is more desirable than vacuum deposition techniques. Solution deposition methods are especially preferred. The formulations of the present invention enable the use of a number of liquid coating techniques. Preferred deposition techniques include, without limitation, dip coating, spin coating, ink jet printing, nozzle printing, letter-press printing, screen printing, gravure printing, doctor blade coating, roller printing, reverse-roller printing, offset lithography printing, dry offset lithography printing, flexographic printing, web printing, spray coating, curtain coating, brush coating, slot dye coating or pad printing.

[0236] Ink jet printing is particularly preferred when high resolution layers and devices needs to be prepared. Selected formulations of the present invention may be applied to prefabricated device substrates by ink jet printing or microdispensing. Preferably industrial piezoelectric print heads such as but not limited to those supplied by Aprion, Hitachi-Koki, InkJet Technology, On Target Technology, Picojet, Spectra, Trident, Xaar may be used to apply the organic semiconductor layer to a substrate. Additionally semi-industrial heads such as those manufactured by Brother, Epson, Konica, Seiko Instruments Toshiba TEC or single nozzle microdispensers such as those produced by Microdrop and Microfab may be used.

[0237] In order to be applied by ink jet printing or microdispensing, the polymers should be first dissolved in a suitable solvent. Solvents must fulfil the requirements stated above and must not have any detrimental effect on the chosen print head. Additionally, solvents should have boiling points >100? C., preferably >140? C. and more preferably >150? C. in order to prevent operability problems caused by the solution drying out inside the print head. Apart from the solvents mentioned above, suitable solvents include substituted and non-substituted xylene derivatives, di-C.sub.1-2-alkyl formamide, substituted and non-substituted anisoles and other phenol-ether derivatives, substituted heterocycles such as substituted pyridines, pyrazines, pyrimidines, pyrrolidinones, substituted and non-substituted N,N-di-C.sub.1-2-alkylanilines and other fluorinated or chlorinated aromatics.

[0238] A preferred solvent for depositing a polymer according to the present invention by ink jet printing comprises a benzene derivative which has a benzene ring substituted by one or more substituents wherein the total number of carbon atoms among the one or more substituents is at least three. For example, the benzene derivative may be substituted with a propyl group or three methyl groups, in either case there being at least three carbon atoms in total. Such a solvent enables an ink jet fluid to be formed comprising the solvent with the compound or polymer, which reduces or prevents clogging of the jets and separation of the components during spraying. The solvent(s) may include those selected from the following list of examples: dodecylbenzene, 1-methyl-4-tert-butylbenzene, terpineol, limonene, isodurene, terpinolene, cymene, diethylbenzene. The solvent may be a solvent mixture, that is a combination of two or more solvents, each solvent preferably having a boiling point >100? C., more preferably >140? C. Such solvent(s) also enhance film formation in the layer deposited and reduce defects in the layer.

[0239] The ink jet fluid (that is mixture of solvent, binder and semiconducting compound) preferably has a viscosity at 20? C. of 1-100 mPa.Math.s, more preferably 1-50 mPa.Math.s and most preferably 1-30 mPa.Math.s.

[0240] The polymers, polymer blends, mixtures and formulations according to the present invention can additionally comprise one or more further components or additives selected for example from surface-active compounds, lubricating agents, wetting agents, dispersing agents, hydrophobing agents, adhesive agents, flow improvers, defoaming agents, deaerators, diluents which may be reactive or non-reactive, auxiliaries, colourants, dyes or pigments, sensitizers, stabilizers, nanoparticles or inhibitors.

[0241] The polymers, polymer blends and mixtures according to the present invention are useful as charge transport, semiconducting, electrically conducting, photoconducting or light emitting material in optical, electrooptical, electronic, electroluminescent or photoluminescent components or devices. In these devices, a polymer, polymer blend or mixture of the present invention is typically applied as a thin layer or film.

[0242] Thus, the present invention also provides the use of the polymer, polymer blend, mixture or layer in an electronic device. The formulation may be used as a high mobility semiconducting material in various devices and apparatus. The formulation may be used, for example, in the form of a semiconducting layer or film. Accordingly, in another aspect, the present invention provides a semiconducting layer for use in an electronic device, the layer comprising a polymer, mixture or polymer blend according to the invention. The layer or film may be less than about 30 microns. For various electronic device applications, the thickness may be less than about 1 micron thick. The layer may be deposited, for example on a part of an electronic device, by any of the aforementioned solution coating or printing techniques.

[0243] The invention additionally provides an electronic device comprising a polymer, polymer blend, mixture or organic semiconducting layer according to the present invention. Especially preferred devices are OFETs, TFTs, ICs, logic circuits, capacitors, RFID tags, OLEDs, OLETs, OPEDs, OPVs, OPDs, solar cells, laser diodes, photoconductors, photodetectors, electrophotographic devices, electrophotographic recording devices, organic memory devices, sensor devices, charge injection layers, Schottky diodes, planarising layers, antistatic films, conducting substrates and conducting patterns.

[0244] Especially preferred electronic device are OFETs, OLEDs, OPV and OPD devices, in particular bulk heterojunction (BHJ) OPV devices. In an OFET, for example, the active semiconductor channel between the drain and source may comprise the layer of the invention. As another example, in an OLED device, the charge (hole or electron) injection or transport layer may comprise the layer of the invention.

[0245] For use in OPV or OPD devices the polymer according to the present invention is preferably used in a formulation that comprises or contains, more preferably consists essentially of, very preferably exclusively of, one or more p-type (electron donor) semiconductor and one or more n-type (electron acceptor) semiconductor. The p-type semiconductor is constituted of a least one polymer according to the present invention. The n-type semiconductor can be an inorganic material such as zinc oxide (ZnO.sub.x), zinc tin oxide (ZTO), titanium oxide (TiO.sub.x), molybdenum oxide (MoO.sub.x), nickel oxide (NiO.sub.x), or cadmium selenide (CdSe), or an organic material such as graphene or a fullerene, a conjugated polymer or substituted fullerene, for example a (6,6)-phenyl-butyric acid methyl ester derivatized methano C.sub.60 fullerene, also known as PCBM-C.sub.60 or C.sub.60PCBM, as disclosed for example in Science 1995, 270, 1789 and having the structure shown below, or structural analogous compounds with e.g. a C.sub.70 fullerene group or an organic polymer (see for example Coakley, K. M. and McGehee, M. D. Chem. Mater. 2004, 16, 4533).

##STR00065##

[0246] Preferably the polymer according to the present invention is blended with an n-type semiconductor such as a fullerene or substituted fullerene of formula XII to form the active layer in an OPV or OPD device wherein,

##STR00066## [0247] C.sub.n denotes a fullerene composed of n carbon atoms, optionally with one or more atoms trapped inside, [0248] Adduct.sup.1 is a primary adduct appended to the fullerene C.sub.n with any connectivity, [0249] Adduct.sup.2 is a secondary adduct, or a combination of secondary adducts, appended to the fullerene C.sub.n with any connectivity, [0250] k is an integer ?1, [0251] and [0252] l is 0, an integer ?1, or a non-integer >0.

[0253] In the formula XII and its subformulae, k preferably denotes 1, 2, 3 or, 4, very preferably 1 or 2.

[0254] The fullerene C.sub.n in formula XII and its subformulae may be composed of any number n of carbon atoms Preferably, in the compounds of formula XII and its subformulae the number of carbon atoms n of which the fullerene C.sub.n is composed is 60, 70, 76, 78, 82, 84, 90, 94 or 96, very preferably 60 or 70.

[0255] The fullerene C.sub.n in formula XII and its subformulae is preferably selected from carbon based fullerenes, endohedral fullerenes, or mixtures thereof, very preferably from carbon based fullerenes.

[0256] Suitable and preferred carbon based fullerenes include, without limitation, (C.sub.60-lh)[5,6]fullerene, (C.sub.70-D5h)[5,6]fullerene, (C.sub.76-D2*)[5,6]fullerene, (C.sub.84-D2*)[5,6]fullerene, (C.sub.84-D2d)[5,6]fullerene, or a mixture of two or more of the aforementioned carbon based fullerenes.

[0257] The endohedral fullerenes are preferably metallofullerenes. Suitable and preferred metallofullerenes include, without limitation, La@C.sub.60, La@C.sub.82, Y@C.sub.82, Sc.sub.3N@C.sub.80, Y.sub.3N@C.sub.80, Sc.sub.3C.sub.2@C.sub.80 or a mixture of two or more of the aforementioned metallofullerenes.

[0258] Preferably the fullerene C.sub.n is substituted at a [6,6] and/or [5,6] bond, preferably substituted on at least one [6,6] bond.

[0259] Primary and secondary adduct, named Adduct in formula XII and its subformulae, is preferably selected from the following formulae

##STR00067## ##STR00068## ##STR00069## ##STR00070##

[0260] wherein C.sub.n is as defined in formula XII, [0261] Ar.sup.S1, Ar.sup.S2 denote, independently of each other, an arylene or heteroarylene group with 5 to 20, preferably 5 to 15, ring atoms, which is mono- or polycyclic, and which is optionally substituted by one or more identical or different substituents having one of the meanings of L as defined above and below, and

[0262] R.sup.S1, R.sup.S2, R.sup.S3, R.sup.S4, R.sup.S5 and R.sup.S6 independently of each other denote H, CN or have one of the meanings of L as defined above and below.

[0263] Preferred compounds of formula XII are selected from the following subformulae:

##STR00071## ##STR00072##

[0264] wherein C.sub.n, k and l are as defined in formula XII, and

[0265] R.sup.S1, R.sup.S2, R.sup.S3, R.sup.S4 R.sup.S5 and R.sup.S6 independently of each other denote H or have one of the meanings of L as defined above and below.

[0266] Also preferably the polymer according to the present invention is blended with other type of n-type semiconductor such as graphene, a metal oxide, like for example, ZnOx, TiOx, ZTO, MoOx, NiOx, quantum dots, like for example, CdSe or CdS, or a conjugated polymer, like for example a polynaphthalenediimide or polyperylenediimide as described, for example, in WO2013142841 A1 to form the active layer in an OPV or OPD device.

[0267] The device preferably further comprises a first transparent or semi-transparent electrode on a transparent or semi-transparent substrate on one side of the active layer, and a second metallic or semi-transparent electrode on the other side of the active layer.

[0268] Preferably, the active layer according to the present invention is further blended with additional organic and inorganic compounds to enhance the device properties. For example, metal particles such as Au or Ag nanoparticles or Au or Ag nanoprism for enhancements in light harvesting due to near-field effects (i.e. plasmonic effect) as described, for example in Adv. Mater. 2013, 25 (17), 2385-2396 and Adv. Ener. Mater. 10.1002/aenm.201400206, a molecular dopant such as 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane for enhancement in photoconductivity as described, for example in Adv. Mater. 2013, 25(48), 7038-7044, or a stabilising agent consisting of a UV absorption agent and/or anti-radical agent and/or antioxidant agent such as 2-hydroxybenzophenone, 2-hydroxyphenylbenzotriazole, oxalic acid anilides, hydroxyphenyl triazines, merocyanines, hindered phenol, N-aryl-thiomorpholine, N-aryl-thiomorpholine-1-oxide, N-aryl-thiomorpholine-1,1-dioxide, N-aryl-thiazolidine, N-aryl-thiazolidine-1-oxide, N-aryl-thiazolidine-1,1-dioxide and 1,4-diazabicyclo[2.2.2]octane as described, for example, in WO2012095796 A1 and in WO2013021971 A1.

[0269] The device preferably may further comprise a UV to visible photo-conversion layer such as described, for example, in J. Mater. Chem. 2011, 21, 12331 or a NIR to visible or IR to NIR photo-conversion layer such as described, for example, in J. Appl. Phys. 2013, 113, 124509.

[0270] Further preferably the OPV or OPD device comprises, between the active layer and the first or second electrode, one or more additional buffer layers acting as hole transporting layer and/or electron blocking layer, which comprise a material such as metal oxides, like for example, ZTO, MoO.sub.x, NiO.sub.x, a doped conjugated polymer, like for example PEDOT:PSS and polypyrrole-polystyrene sulfonate (PPy:PSS), a conjugated polymer, like for example polytriarylamine (PTAA), an organic compound, like for example substituted triaryl amine derivatives such as N,N-diphenyl-N,N-bis(1-naphthyl)(1,1-biphenyl)-4,4diamine (NPB), N,N-diphenyl-N,N-(3-methylphenyl)-1,1-biphenyl-4,4-diamine (TPD), graphene based materials, like for example, graphene oxide and graphene quantum dots or alternatively as hole blocking layer and/or electron transporting layer, which comprise a material such as metal oxide, like for example, ZnO.sub.x, TiO.sub.x, AZO (aluminium doped zinc oxide), a salt, like for example LiF, NaF, CsF, a conjugated polymer electrolyte, like for example poly[3-(6-trimethylammoniumhexyl)thiophene], poly(9,9-bis(2-ethylhexyl)-fluorene]-b-poly[3-(6-trimethylammoniumhexyl)thiophene], or poly[(9,9-bis(3-(N,N-dimethylamino)propyl)-2,7-fluorene)-alt-2,7-(9,9-dioctylfluorene)], a polymer, like for example poly(ethyleneimine) or crosslinked N-containing compound derivatives or an organic compound, like for example tris(8-quinolinolato)-aluminium(III) (Alq.sub.3), phenanthroline derivative or C.sub.60 or C.sub.70 based fullerenes, like for example, as described in Adv. Energy Mater. 2012, 2, 82-86.

[0271] In a blend or mixture of a polymer according to the present invention with a fullerene or modified fullerene, the ratio polymer:fullerene is preferably from 5:1 to 1:5 by weight, more preferably from 2:1 to 1:3 by weight, most preferably 1:1 to 1:2 by weight. A polymeric binder may also be included, from 5 to 95% by weight. Examples of binder include polystyrene (PS), polypropylene (PP) and polymethylmethacrylate (PMMA).

[0272] To produce thin layers in BHJ OPV devices the polymers, polymer blends or mixtures of the present invention may be deposited by any suitable method. Liquid coating of devices is more desirable than vacuum deposition techniques. Solution deposition methods are especially preferred. The formulations of the present invention enable the use of a number of liquid coating techniques. Preferred deposition techniques include, without limitation, dip coating, spin coating, ink jet printing, nozzle printing, letter-press printing, screen printing, gravure printing, doctor blade coating, roller printing, reverse-roller printing, offset lithography printing, dry offset lithography printing, flexographic printing, web printing, spray coating, curtain coating, brush coating, slot dye coating or pad printing. For the fabrication of OPV devices and modules area printing method compatible with flexible substrates are preferred, for example slot dye coating, spray coating and the like.

[0273] Suitable solutions or formulations containing a blend or mixture of a polymer according to the present invention with a fullerene or modified fullerene like PCBM are preferably prepared. In the preparation of such a formulation, suitable solvents are preferably selected to ensure full dissolution of both component, p-type and n-type and take into account the boundary conditions (for example rheological properties) introduced by the chosen printing method.

[0274] Organic solvent are generally used for this purpose. Typical solvents can be aromatic solvents, halogenated solvents or chlorinated solvents, including chlorinated aromatic solvents. Examples include, but are not limited to dichloromethane, trichloromethane, tetrachloromethane, chlorobenzene, o-dichlorobenzene, 1,2,4-trichlorobenzene, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, 1,8-diiodooctane, 1-chloronaphthalene, 1,8-octane-dithiol, anisole, 2,5-di-methylanisole, 2,4-dimethylanisole, toluene, o-xylene, m-xylene, p-xylene, mixture of xylene o-, m-, and p-isomers, 1,2,4-trimethylbenzene, mesitylene, cyclohexane, 1-methylnaphthalene, 2-methylnaphthalene, 1,2-dimethylnaphthalene, tetraline, decaline, indane, 1-methyl-4-(1-methylethenyl)-cyclohexene (d-Limonene), 6,6-dimethyl-2-methylenebicyclo[3.1.1]heptanes (?-pinene), methyl benzoate, ethyl benzoate, nitrobenzene, benzaldehyde, tetrahydrofuran, 1,4-dioxane, 1,3-dioxane, morpholine, acetone, methylethylketone, ethyl acetate, n-butyl acetate, N,N-dimethylformamide, dimethylacetamide, dimethylsulfoxide and/or mixtures thereof.

[0275] The OPV device can for example be of any type known from the literature (see e.g. Waldauf et al., Appl. Phys. Lett., 2006, 89, 233517).

[0276] A first preferred OPV device according to the invention comprises the following layers (in the sequence from bottom to top): [0277] optionally a substrate, [0278] a high work function electrode, preferably comprising a metal oxide, like for example ITO and FTO, serving as anode, [0279] an optional conducting polymer layer or hole transport layer, preferably comprising an organic polymer or polymer blend, for example PEDOT:PSS (poly(3,4-ethylenedioxythiophene):poly(styrene-sulfonate), substituted triaryl amine derivatives, for example, TBD (N,N-dyphenyl-N-N-bis(3-methylphenyl)-1,1biphenyl-4,4-diamine) or NBD (N,N-dyphenyl-N-N-bis(1-napthylphenyl)-1,1biphenyl-4,4-diamine), [0280] a layer, also referred to as active layer, comprising of at least one p-type and at least one n-type organic semiconductor, which can exist for example as a p-type/n-type bilayer or as distinct p-type and n-type layers, or as blend or p-type and n-type semiconductor, forming a BHJ, [0281] optionally a layer having electron transport properties, for example comprising LiF, TiO.sub.x, ZnO.sub.x, PFN, a poly(ethyleneimine) or crosslinked nitrogen containing compound derivatives or a phenanthroline derivatives [0282] a low work function electrode, preferably comprising a metal like for example aluminum, serving as cathode, [0283] wherein at least one of the electrodes, preferably the anode, is transparent to visible and/or NIR light, and [0284] wherein at least one p-type semiconductor is a polymer according to the present invention.

[0285] A second preferred OPV device according to the invention is an inverted OPV device and comprises the following layers (in the sequence from bottom to top): [0286] optionally a substrate, [0287] a high work function metal or metal oxide electrode, comprising for example ITO and FTO, serving as cathode, [0288] a layer having hole blocking properties, preferably comprising a metal oxide like TiO.sub.x or ZnO.sub.x, or comprising an organic compound such as polymer like poly(ethyleneimine) or crosslinked nitrogen containing compound derivatives or phenanthroline derivatives, [0289] an active layer comprising at least one p-type and at least one n-type organic semiconductor, situated between the electrodes, which can exist for example as a p-type/n-type bilayer or as distinct p-type and n-type layers, or as blend or p-type and n-type semiconductor, forming a BHJ, [0290] an optional conducting polymer layer or hole transport layer, preferably comprising an organic polymer or polymer blend, for example of PEDOT:PSS or substituted triaryl amine derivatives, for example, TBD or NBD, [0291] an electrode comprising a high work function metal like for example silver, serving as anode, [0292] wherein at least one of the electrodes, preferably the cathode, is transparent to visible and/or NIR light, and [0293] wherein at least one p-type semiconductor is a polymer according to the present invention.

[0294] In the OPV devices of the present invention the p-type and n-type semiconductor materials are preferably selected from the materials, like the polymer/fullerene systems or polymer/polymer systems, as described above

[0295] When the active layer is deposited on the substrate, it forms a BHJ that phase separates at nanoscale level. For discussion on nanoscale phase separation see Dennler et al, Proceedings of the IEEE, 2005, 93 (8), 1429 or Hoppe et al, Adv. Func. Mater, 2004, 14(10), 1005. An optional annealing step may be then necessary to optimize blend morphology and consequently OPV device performance.

[0296] Another method to optimize device performance is to prepare formulations for the fabrication of OPV (BHJ) devices that may include high boiling point additives to promote phase separation in the right way. 1,8-Octanedithiol, 1,8-diiodooctane, nitrobenzene, 1-chloronaphthalene, N,N-dimethylformamide, dimethylacetamide, dimethylsulfoxide and other additives have been used to obtain high-efficiency solar cells. Examples are disclosed in J. Peet. et al, Nat. Mater., 2007, 6. 497 or Fr?chet et al. J. Am. Chem. Soc., 2010, 132, 7595-7597.

[0297] The polymers, polymer blends, mixtures and layers of the present invention are also suitable for use in an OFET as the semiconducting channel. Accordingly, the invention also provides an OFET comprising a gate electrode, an insulating (or gate insulator) layer, a source electrode, a drain electrode and an organic semiconducting channel connecting the source and drain electrodes, wherein the organic semiconducting channel comprises a polymer, polymer blend, mixture or organic semiconducting layer according to the present invention. Other features of the OFET are well known to those skilled in the art.

[0298] OFETs where an OSC material is arranged as a thin film between a gate dielectric and a drain and a source electrode, are generally known, and are described for example in U.S. Pat. No. 5,892,244, U.S. Pat. No. 5,998,804, U.S. Pat. No. 6,723,394 and in the references cited in the background section. Due to the advantages, like low cost production using the solubility properties of the compounds according to the invention and thus the processibility of large surfaces, preferred applications of these FETs are such as integrated circuitry, TFT displays and security applications.

[0299] The gate, source and drain electrodes and the insulating and semiconducting layer in the OFET device may be arranged in any sequence, provided that the source and drain electrode are separated from the gate electrode by the insulating layer, the gate electrode and the semiconductor layer both contact the insulating layer, and the source electrode and the drain electrode both contact the semiconducting layer.

[0300] An OFET device according to the present invention preferably comprises: [0301] a source electrode, [0302] a drain electrode, [0303] a gate electrode, [0304] a semiconducting layer, [0305] one or more gate insulator layers, [0306] optionally a substrate.

[0307] wherein the semiconductor layer preferably comprises a polymer, polymer blend or mixture according to the present invention.

[0308] The OFET device can be a top gate device or a bottom gate device. Suitable structures and manufacturing methods of an OFET device are known to the skilled in the art and are described in the literature, for example in US 2007/0102696 A1.

[0309] The gate insulator layer preferably comprises a fluoropolymer, like e.g. the commercially available Cytop 809M? or Cytop 107M? (from Asahi Glass).

[0310] Preferably the gate insulator layer is deposited, e.g. by spin-coating, doctor blading, wire bar coating, spray or dip coating or other known methods, from a formulation comprising an insulator material and one or more solvents with one or more fluoro atoms (fluorosolvents), preferably a perfluorosolvent. A suitable perfluorosolvent is e.g. FC75? (available from Acros, catalogue number 12380). Other suitable fluoropolymers and fluorosolvents are known in prior art, like for example the perfluoropolymers Teflon AF? 1600 or 2400 (from DuPont) or Fluoropel? (from Cytonix) or the perfluorosolvent FC 43? (Acros, No. 12377).

[0311] Especially preferred are organic dielectric materials having a low permittivity (or dielectric constant) from 1.0 to 5.0, very preferably from 1.8 to 4.0 (low k materials), as disclosed for example in US 2007/0102696 A1 or U.S. Pat. No. 7,095,044.

[0312] In security applications, OFETs and other devices with semiconducting materials according to the present invention, like transistors or diodes, can be used for RFID tags or security markings to authenticate and prevent counterfeiting of documents of value like banknotes, credit cards or ID cards, national ID documents, licenses or any product with monetary value, like stamps, tickets, shares, cheques etc.

[0313] Alternatively, the polymers, polymer blends and mixtures according to the invention can be used in OLEDs, e.g. as the active display material in a flat panel display applications, or as backlight of a flat panel display like e.g. a liquid crystal display. Common OLEDs are realized using multilayer structures. An emission layer is generally sandwiched between one or more electron-transport and/or hole-transport layers. By applying an electric voltage electrons and holes as charge carriers move towards the emissive layer where their recombination leads to the excitation and hence luminescence of the lumophor units contained in the emission layer.

[0314] The polymers, polymer blends and mixtures according to the invention can be employed in one or more of a buffer layer, electron or hole transport layer, electron or hole blocking layer and emissive layer, corresponding to their electrical and/or optical properties. Furthermore their use within the emissive layer is especially advantageous, if the compounds, materials and films according to the invention show electroluminescent properties themselves or comprise electroluminescent groups or compounds. The selection, characterization as well as the processing of suitable monomeric, oligomeric and polymeric compounds or materials for the use in OLEDs is generally known by a person skilled in the art, see, e.g., M?ller et al, Synth. Metals, 2000, 111-112, 31-34, Alcala, J. Appl. Phys., 2000, 88, 7124-7128 and the literature cited therein.

[0315] According to another use, the polymers, polymer blends and mixtures according to this invention, especially those showing photoluminescent properties, may be employed as materials of light sources, e.g. in display devices, as described in EP 0 889 350 A1 or by C. Weder et al., Science, 1998, 279, 835-837.

[0316] A further aspect of the invention relates to both the oxidised and reduced form of a polymer according to this invention. Either loss or gain of electrons results in formation of a highly delocalised ionic form, which is of high conductivity. This can occur on exposure to common dopants.

[0317] Suitable dopants and methods of doping are known to those skilled in the art, e.g. from EP 0 528 662, U.S. Pat. No. 5,198,153 or WO 96/21659.

[0318] The doping process typically implies treatment of the semiconductor material with an oxidating or reducing agent in a redox reaction to form delocalised ionic centres in the material, with the corresponding counterions derived from the applied dopants. Suitable doping methods comprise for example exposure to a doping vapor in the atmospheric pressure or at a reduced pressure, electrochemical doping in a solution containing a dopant, bringing a dopant into contact with the semiconductor material to be thermally diffused, and ion-implantation of the dopant into the semiconductor material.

[0319] When electrons are used as carriers, suitable dopants are for example halogens (e.g., I.sub.2, Cl.sub.2, Br.sub.2, ICl, ICl.sub.3, IBr and IF), Lewis acids (e.g., PF.sub.5, AsF.sub.5, SbF.sub.5, BF.sub.3, BCl.sub.3, SbCl.sub.5, BBr.sub.3 and SO.sub.3), protonic acids, organic acids, or amino acids (e.g., HF, HCl, HNO.sub.3, H.sub.2SO.sub.4, HClO.sub.4, FSO.sub.3H and ClSO.sub.3H), transition metal compounds (e.g., FeCl.sub.3, FeOCl, Fe(ClO.sub.4).sub.3, Fe(4-CH.sub.3C.sub.6H.sub.4SO.sub.3).sub.3, TiCl.sub.4, ZrCl.sub.4, HfCl.sub.4, NbF.sub.5, NbCl.sub.5, TaCl.sub.5, MoF.sub.5, MoCl.sub.5, WF.sub.5, WCl.sub.6, UF.sub.6 and LnCl.sub.3 (wherein Ln is a lanthanoid), anions (e.g., Cl.sup.?, Br.sup.?, I.sup.?, I.sub.3.sup.?, HSO.sub.4.sup.?, SO.sub.4.sup.2?, NO.sub.3.sup.?, ClO.sub.4.sup.?, BF.sub.4.sup.?, PF.sub.6.sup.?, AsF.sub.6.sup.?, SbF.sub.6.sup.?, FeCl.sub.4.sup.?, Fe(CN).sub.6.sup.3?, and anions of various sulfonic acids, such as aryl-SO.sub.3.sup.?). When holes are used as carriers, examples of dopants are cations (e.g., H.sup.+, Li.sup.+, Na.sup.+, K.sup.+, Rb.sup.+ and Cs.sup.+), alkali metals (e.g., Li, Na, K, Rb, and Cs), alkaline-earth metals (e.g., Ca, Sr, and Ba), O.sub.2, XeOF.sub.4, (NO.sub.2.sup.+) (SbF.sub.6.sup.?), (NO.sub.2.sup.+) (SbCl.sub.6.sup.?), (NO.sub.2.sup.+) (BF.sub.4.sup.?), AgClO.sub.4, H.sub.2IrCl.sub.6, La(NO.sub.3).sub.3.6H.sub.2O, FSO.sub.2OOSO.sub.2F, Eu, acetylcholine, R.sub.4N.sup.+, (R is an alkyl group), R.sub.4P.sup.+ (R is an alkyl group), R.sub.6As.sup.+ (R is an alkyl group), and R.sub.3S.sup.+ (R is an alkyl group).

[0320] The conducting form of a polymer of the present invention can be used as an organic metal in applications including, but not limited to, charge injection layers and ITO planarising layers in OLED applications, films for flat panel displays and touch screens, antistatic films, printed conductive substrates, patterns or tracts in electronic applications such as printed circuit boards and condensers.

[0321] The polymers, polymer blends and mixtures according to the present invention may also be suitable for use in organic plasmon-emitting diodes (OPEDs), as described for example in Koller et al., Nat. Photonics, 2008, 2, 684.

[0322] According to another use, the polymers according to the present invention can be used alone or together with other materials in or as alignment layers in LCD or OLED devices, as described for example in US 2003/0021913. The use of charge transport polymers according to the present invention can increase the electrical conductivity of the alignment layer. When used in an LCD, this increased electrical conductivity can reduce adverse residual dc effects in the switchable LCD cell and suppress image sticking or, for example in ferroelectric LCDs, reduce the residual charge produced by the switching of the spontaneous polarisation charge of the ferroelectric LCs. When used in an OLED device comprising a light emitting material provided onto the alignment layer, this increased electrical conductivity can enhance the electroluminescence of the light emitting material. The polymers according to the present invention having mesogenic or liquid crystalline properties can form oriented anisotropic films as described above, which are especially useful as alignment layers to induce or enhance alignment in a liquid crystal medium provided onto said anisotropic film. The polymers according to the present invention may also be combined with photoisomerisable compounds and/or chromophores for use in or as photoalignment layers, as described in US 2003/0021913 A1.

[0323] According to another use the polymers, polymer blends and mixtures according to the present invention, especially their water-soluble derivatives (for example with polar or ionic side groups) or ionically doped forms, can be employed as chemical sensors or materials for detecting and discriminating DNA sequences. Such uses are described for example in L. Chen, D. W. McBranch, H. Wang, R. Helgeson, F. Wudl and D. G. Whitten, Proc. Natl. Acad. Sci. U.S.A., 1999, 96, 12287; D. Wang, X. Gong, P. S. Heeger, F. Rininsland, G. C. Bazan and A. J. Heeger, Proc. Natl. Acad. Sci. U.S.A., 2002, 99, 49; N. DiCesare, M. R. Pinot, K. S. Schanze and J. R. Lakowicz, Langmuir, 2002, 18, 7785; D. T. McQuade, A. E. Pullen, T. M. Swager, Chem. Rev., 2000, 100, 2537.

[0324] Unless the context clearly indicates otherwise, as used herein plural forms of the terms herein are to be construed as including the singular form and vice versa.

[0325] Throughout the description and claims of this specification, the words comprise and contain and variations of the words, for example comprising and comprises, mean including but not limited to, and are not intended to (and do not) exclude other components.

[0326] It will be appreciated that variations to the foregoing embodiments of the invention can be made while still falling within the scope of the invention.

[0327] Each feature disclosed in this specification, unless stated otherwise, may be replaced by alternative features serving the same, equivalent or similar purpose. Thus, unless stated otherwise, each feature disclosed is one example only of a generic series of equivalent or similar features.

[0328] All of the features disclosed in this specification may be combined in any combination, except combinations where at least some of such features and/or steps are mutually exclusive. In particular, the preferred features of the invention are applicable to all aspects of the invention and may be used in any combination. Likewise, features described in non-essential combinations may be used separately (not in combination).

[0329] Above and below, unless stated otherwise percentages are percent by weight and temperatures are given in degrees Celsius. Values of the dielectric constant ? (permittivity) refer to values taken at 20? C. and 1,000 Hz.

[0330] The invention will now be described in more detail by reference to the following examples, which are illustrative only and do not limit the scope of the invention.

A) MONOMER AND POLYMER EXAMPLES

Example M1

[0331] Monomer 1 was prepared as follows:

Benzo[1,2-d;4,5-d]bisthiazole-2,6-dicarboxylic acid diethyl ester (1.1)

[0332] ##STR00073##

[0333] 2,5-Diamino-benzene-1,4-dithiol hydrochloride (5.00 g; 20.39 mmol; 1.00 eq.) is suspended in anhydrous N,N-dimethylformamide (37 cm.sup.3) at 50? C. Anhydrous pyridine (3.39 g; 3.49 cm.sup.3; 42.82 mmol; 2.10 eq.) is slowly added and the mixture stirred at 50? C. for 1 hour under a flow of nitrogen. The clear yellow solution obtained is transferred to a flask containing triethoxy-acetic acid ethyl ester (16.62 g; 75.45 mmol; 3.70 eq.) and yttrium(III) triflate (0.57 g; 1.02 mmol; 0.05 eq.). Slow precipitation is observed. The mixture is stirred at 60? C. for 72 hours under nitrogen. Subsequently, the mixture is cooled to room temperature. The precipitate is isolated by filtration and washed copiously with methanol, yielding the product as a yellow powder (4.07 g, 59.3%).

[0334] .sup.1H NMR (300 MHz, Chloroform-d) ?: 8.84 (s, 2H), 4.60 (q, 4h), 1.52 (t, 6H).

Benzo[1,2-d;4,5-d]bisthiazole-2,6-dicarboxylic acid didodecyl ester (1.2)

[0335] ##STR00074##

[0336] Benzo[1,2-d;4,5-d]bisthiazole-2,6-dicarboxylic acid diethyl ester (4.07 g; 12.10 mmol; 1.00 eq.), toluene-4-sulfonic acid (0.42 g; 2.42 mmol; 0.20 eq.) and dodecan-1-ol (4.73 g; 25.41 mmol; 2.10 eq.) are dissolved in o-xylene (200 cm.sup.3). Dean-Stark apparatus is attached to the flask and mixture is heated at 140? C. for 16 hours. The solvent is removed in vacuo, and another portion of dodecan-1-ol (4.73 g; 25.41 mmol; 2.10 eq.), toluene-4-sulfonic acid (0.42 g; 2.42 mmol; 0.20 eq.) and o-xylene (200 cm.sup.3) are added and the mixture refluxed under Dean-Stark trap for 16 hours. Subsequently, the solution is cooled to ca. 60? C. and passed through a short silica plug. The solvent is removed in vacuo and the residue is recrystallized from boiling petroleum ether (100 cm.sup.3, b.p. 80-100? C.), yielding the product as a light yellow powder (4.89 g; 65.5%).

[0337] .sup.1H NMR (400 MHz, Chloroform-d) ?: 8.84 (s, 2H), 4.52 (t, 4H, J=6.84 Hz), 1.88 (m, 4H), 1.53-1.20 (m, 36H), 0.86 (t, 4H, J=7.0 Hz).

4,8-Dibromo-benzo[1,2-d;4,5-d]bisthiazole-2,6-dicarboxylic acid didodecyl ester (1)

[0338] ##STR00075##

[0339] Benzo[1,2-d;4,5-d]bisthiazole-2,6-dicarboxylic acid didodecyl ester (1.60 g; 2.59 mmol; 1.00 eq.) is dissolved in anhydrous N,N-dimethylformamide (24.0 cm.sup.3), stirred at 60? C. for 30 minutes. Subsequently, bromine (16.99 g; 5.45 cm.sup.3; 4 eq.) is added by syringe over a period of 5 minutes. The solution is then heated at 100-105? C. for 30 minutes, under nitrogen. The exhaust fumes are passed through a bubbler filled with aqueous sodium sulphite. Subsequently, the reaction is quenched by pouring into 200 cm.sup.3 saturated aq. Na.sub.2SO.sub.3 and filtered. The solid is washed with water and methanol and purified by silica gel column chromatography (eluent: dichloromethane), to yield the product as yellow crystals (837 mg, 41.7%).

[0340] .sup.1H NMR (300 MHz, Chloroform-d) ? 4.51 (t, J=6.83 Hz. 4H), 1.94-1.80 (m, 4H), 1.52-1.19 (m, 36H), 0.87 (t, J=7.05 Hz, 6H).

Example M2

[0341] Monomer 2 was prepared as follows:

Benzo[1,2-d;4,5-d]bisthiazole-2,6-dicarboxylic acid bis-(3,7-dimethyl-octyl) ester (2.1)

[0342] ##STR00076##

[0343] Benzo[1,2-d;4,5-d]bisthiazole-2,6-dicarboxylic acid diethyl ester (0.99 g; 2.94 mmol; 1.00 eq.), toluene-4-sulfonic acid (0.10 g; 0.589 mmol; 0.20 eq.) and 3,7-dimethyl-octan-1-ol (0.98 g; 6.18 mmol; 2.10 eq.) are dissolved in o-xylene (50 cm.sup.3). Dean-Stark apparatus is attached to the flask and the mixture is heated at 140? C. for 16 hours. The solvents are removed in vacuo and the residue is redissolved in dichloromethane (50 cm.sup.3). The product is precipitated by addition of methanol (50 cm.sup.3), water (200 cm.sup.3) and additional methanol (until disappearance of the 3,7-dimethyl-octan-1-ol phase), collected by filtration and purified by silica gel column chromatography (eluent: petroleum ether b.p. 40-60? C./dichloromethane). Yield: 1.06 g (64.5%).

4,8-Dibromo-benzo[1,2-d;4,5-d]bisthiazole-2,6-dicarboxylic acid bis-(3,7-dimethyl-octyl) ester (2)

[0344] ##STR00077##

[0345] Benzo[1,2-d;4,5-d]bisthiazole-2,6-dicarboxylic acid bis-(3,7-dimethyl-octyl) ester (1.06 g; 1.89 mmol; 1.00 eq.) is dissolved in anhydrous N,N-dimethylformamide (16 cm.sup.3) at 60? C. Bromine (12.38 g; 3.97 cm.sup.3; 77.49 mmol; 41.00 eq.) is added and the solution is heated at 110? C. for 30 minutes under nitrogen. Subsequently, the reaction is quenched by pouring into 200 cm.sup.3 saturated aq. Na.sub.2SO.sub.3 and filtered. The solid is washed with water and methanol and purified by silica gel column chromatography (eluent: petroleum ether/dichloromethane), to yield the product as a light yellow powder (571 mg; 0.79 mmol; 42.0%).

[0346] 1H NMR (500 MHz, Chloroform-d) ? 4.60-4.51 (m, 4H), 1.95-1.87 (m, 2H), 1.73-1.62 (m, 4H), 1.59-1.48 (m, 2H), 1.41-1.13 (m, 12H), 0.99 (d, J=6.4 Hz, 6H), 0.90-0.82 (m, 12H).

Example M3

[0347] Compound 3.1 was prepared as follows:

2,6-Didodecyl-benzo[1,2-d;4,5-d]bisthiazole (3.1)

[0348] ##STR00078##

[0349] To 3-necked flask equipped with a mechanical agitator is added polyphosphoric acid (40 g) and 2,5-diamino-benzene-1,4-dithiol hydrochloride (5.00 g, 20.39 mmol, 1.00 eq). The mixture is stirred and heated at 70? C. and 13 mbar for 5 minutes and at 100? C. and 10 mbar for a further 30 minutes. The mixture is then allowed to cool to 60? C., tridecanoic acid (8.96 g, 41.80 mmol, 2.05 eq.) and phosphorous pentoxide (26.0 g, 91.58 mmol, 4.49 eq.) are added. The mixture is stirred at 100? C. for 30 minutes followed by stirring at 140? C. for 16 hours. Subsequently, the reaction mixture was cooled to 80? C. and water was added (30 cm.sup.3). The mixture was stirred for 1 hour, allowed to cool to 40? C. and dichloromethane (100 cm.sup.3) is added. The phases are separated, the organic phase is washed with aq. sodium hydroxide solution, dried over magnesium sulphate and concentrated in vacuo. The product is obtained as a yellow solid (5.00 g, 46.4%).

[0350] .sup.1H NMR (300 MHz, Chloroform-d) ? 8.38 (s, 1H), 3.13 (t, 4H, J=7.7 Hz), 1.96-1.82 (m, 4H), 1.50-1.20 (m, 18H), 0.88 (t, J=6.7 Hz, 4H).

Example M4

[0351] Monomer 4 was prepared as follows:

2,6-Bis-(1-hexyl-nonyl)-benzo[1,2-d;4,5-d]bisthiazole (4.1)

[0352] ##STR00079##

[0353] To 3-necked flask equipped with a mechanical agitator is added polyphosphoric acid (20.0 g) and 2,5-diamino-benzene-1,4-dithiol hydrochloride (2.50 g; 10.20 mmol; 1.00 eq.)). The mixture is stirred and heated at 100? C. and 10 mbar for 2 hours. The mixture is then allowed to cool to 60? C., 2-hexyl-decanoic acid (5.36 g; 20.90 mmol; 2.05 eq.) and phosphorous pentoxide (13.03 g; 45.88 mmol; 4.50 eq.) are added. The mixture is carefully degassed and stirred at 140? C. for 18 hours, under nitrogen. Subsequently, the reaction mixture is cooled to 80? C. and water was added (50 cm.sup.3). The mixture is extracted with dichloromethane, washed with saturated aq. NaHCO.sub.3, washed with brine, dried over MgSO.sub.4 and filtered. The solvent is removed in vacuo and the residue purified by column chromatography on silica (eluent: petroleum ether/dichloromethane), yielding the product as a yellow oil (4.38 g; 70.1%).

[0354] 1H NMR (300 MHz, Chloroform-d) ?: 8.41 (s, 2H), 3.15 (tt, J=7.2 Hz, 2H), 1.79 (m, 8H, CHCH2), 1.2-1.4 (m, 40H), 0.8-0.9 (m, 12H).

4,8-Dibromo-2,6-bis-(1-hexyl-nonyl)-benzo[1,2-d;4,5-d]bisthiazole (4)

[0355] ##STR00080##

[0356] 2,6-Bis-(1-hexyl-nonyl)-benzo[1,2-d;4,5-d]bisthiazole (4.38 g; 7.14 mmol; 1.00 eq.) is dissolved in anhydrous N,N-dimethylformamide (75 cm.sup.3). Bromine (46.8 g; 15.0 cm.sup.3; 292.9 mmol; 41.0 eq.) is added and the solution is heated at 110? C. for 30 minutes under nitrogen. Subsequently, the reaction is quenched by pouring into 200 cm.sup.3 saturated aq. Na.sub.2SO.sub.3. The reaction mixture is extracted with dichloromethane (2?100 cm.sup.3), combined organic phases washed with water, dried over anhydrous magnesium sulphate and filtered. The solvent is removed in vacuo and the residue purified by silica gel column chromatography (eluent: petroleum ether b.p. 40-60? C./dichloromethane), yielding the product as a yellow oil (2.26 g, 41.0%).

[0357] 1H NMR (400 MHz, Chloroform-d) ? 3.23 (m, 2H), 1.77 (m, 8H), 1.2-1.4 (m, 40H), 0.8-0.9 (m, 12H).

Example M5

[0358] Monomer 5 was prepared as follows.

2,6-Bis-(3-ethyl-heptyl)-benzo[1,2-d;4,5-d]bisthiazole (5.1)

[0359] ##STR00081##

[0360] To 3-necked flask equipped with a mechanical agitator is added polyphosphoric acid (48 g) and 2,5-diamino-benzene-1,4-dithiol hydrochloride (6.00 g, 24.47 mmol, 1.00 eq). The mixture is stirred and heated at 70? C. and 13 mbar for 5 minutes and at 100? C. and 10 mbar for a further 30 minutes. The mixture is then allowed to cool to 60? C., 4-ethyl-octanoic acid (8.64 g, 50.16 mmol, 2.05 eq.) and phosphorous pentoxide (31.26 g, 110.12 mmol, 4.49 eq.) are added. The mixture is stirred at 100? C. for 30 minutes followed by stirring at 140? C. for 16 hours. Subsequently, the reaction mixture was cooled to 80? C. and water was added (30 cm.sup.3). The mixture was stirred for 1 hour, allowed to cool to 40? C. and dichloromethane (100 cm.sup.3) is added. The phases are separated, the organic phase is washed with aq. sodium hydroxide solution, dried over magnesium sulphate, passed through a silica plug and concentrated in vacuo. The product is obtained as a pale brown solid (5.25 g, 48.3%).

[0361] .sup.1H NMR (400 MHz, Chloroform-d) ? 8.38 (s, 2H), 3.16-3.07 (m, 4H), 1.91-1.81 (m, 4H), 1.47-1.36 (m, 8H), 1.36-1.22 (m, 10H), 0.96-0.84 (m, 12H).

4,8-Dibromo-2,6-bis-(3-ethyl-heptyl)-benzo[1,2-d;4,5-d]bisthiazole (5.2)

[0362] ##STR00082##

[0363] 2,6-Bis-(3-ethyl-heptyl)-benzo[1,2-d;4,5-d]bisthiazole (5.25 g; 11.80 mmol; 1.00 eq.) is dissolved in anhydrous N,N-dimethylformamide (125 cm.sup.3). Bromine (77.35 g; 24.8 cm.sup.3; 483.99 mmol; 41.0 eq.) is added and the solution is heated at 110? C. for 10 minutes under nitrogen. Subsequently, the reaction is quenched by pouring into 200 cm.sup.3 saturated aq. Na.sub.2SO.sub.3. The product precipitates and is collected by extraction with DCM. The crude product dissolved in petrol:DCM (roughly 1:4) and passed through a silica plug, the solvents removed, the residue dissolved in warm petrol and purified by column chromatography on silica (eluent: petroleum ether b.p. 40-60? C./dichloromethane), yielding the product as a yellow oil (2.30 g, 32.0%).

[0364] .sup.1H NMR (400 MHz, Chloroform-d) ? 3.16-3.01 (m, 4H), 1.77 (dt, J=11.6, 6.3 Hz, 2H), 1.54-1.38 (m, 8H), 1.38-1.20 (m, 12H), 0.94-0.76 (m, 12H).

4,8-Bis-(4-dodecyl-thiophen-2-yl)-2,6-bis-(3-ethyl-heptyl)-benzo[1,2-d;4,5-d]bisthiazole (5.3)

[0365] ##STR00083##

[0366] 4,8-Dibromo-2,6-bis-(3-ethyl-heptyl)-benzo[1,2-d;4,5-d]bisthiazole (1.10 g; 1.83 mmol; 1.00 eq.), tributyl-(4-dodecyl-thiophen-2-yl)-stannane (2.27 g; 4.20 mmol; 2.30 eq.), Pd2(dba)3 (0.13 g; 0.15 mmol; 0.08 eq.) and tri-o-tolyl-phosphane (0.09 g; 0.29 mmol; 0.16 eq.) are placed into round bottom flask and degassed for 15 minutes. Degassed toluene (13 cm.sup.3) is added and the reaction mixture is further degassed for 30 mins. The reaction mixture is heated at 120? C. overnight. After cooling to room temperature, the reaction mixture is precipitated into methanol (150 cm.sup.3). A fine red precipitate is formed, and a dark, oily liquid phase appears on the bottom of the flask. The fine precipitate is filtered off (glass fibre membrane, suction), redissolved in cyclohexane and purified on column (Biotage, 100 g cartridge, petroleum ether/dichloromethane followed by Biotage, 100 g cartridge, petroleum ether isocratic) to yield the product as an off-white solid (27% yield).

[0367] .sup.1H NMR (400 MHz, Chloroform-d) ? 7.00 (d, J=1.4 Hz, 2H, thiophene C.sub.aromH), 6.79 (d, J=1.4 Hz, 2H, thiophene C.sub.aromH), 2.59 (t, J=7.7 Hz, 4H), 1.64 (m, 4H), 1.28 (s, 74H), 0.95-0.86 (m, 6H).

4,8-Bis-(5-bromo-4-dodecyl-thiophen-2-yl)-2,6-bis-(3-ethyl-heptyl)-benzo[1,2-d;4,5-d]bisthiazole (5)

[0368] ##STR00084##

[0369] To a round bottom flask is added 4,8-bis-(4-dodecyl-thiophen-2-yl)-2,6-bis-(3-ethyl-heptyl)-benzo[1,2-d;4,5-d]bisthiazole (352.00 mg; 0.37 mmol; 1.00 eq.), chloroform (8.71 cm.sup.3), acetic acid (2.90 cm.sup.3). The mixture is stirred at room temperature. 1-Bromo-pyrrolidine-2,5-dione (139.13 mg; 0.78 mmol; 2.10 eq.) is added in one portion and the mixture stirred until dissolution and then left at room temperature for 6 days. Water (50 cm.sup.3) is added and the product is extracted with petroleum ether (200 cm.sup.3). The crude material is purified on column (Biotage, 100 g cartridge, petroleum ether) to yield product as a solid.

[0370] .sup.1H NMR (400 MHz, Chloroform-d) ? 6.77 (s, 2H, C.sub.aromH), 2.51 (d, J=7.7 Hz, 4H), 1.62-1.50 (m, 8H), 1.35-1.20 (m, 68H), 0.88 (t, J=6.7 Hz, 8H).

Example M6

[0371] Compound 6 was prepared as follows

4,8-Bis-(4-dodecyl-thiophen-2-yl)-benzo[1,2-d;4,5-d]bisthiazole-2,6-dicarboxylic acid didodecyl ester (6)

[0372] ##STR00085##

[0373] 4,8-Dibromo-benzo[1,2-d;4,5-d]bisthiazole-2,6-dicarboxylic acid didodecyl ester (1.00 g; 1.29 mmol; 1.00 eq.), tributyl-(4-dodecyl-thiophen-2-yl)-stannane (2.10 g; 3.87 mmol; 3.00 eq.), PdCl2(PPh3)2 (36.34 mg; 0.05 mmol; 0.04 eq.) are charged into a round-bottomed flask and degassed. N,N-Dimethylformamide (24 cm.sup.3) is added and the mixture is degassed for further 10 minutes and heated to 120? C. for 2 h under nitrogen atmosphere with vigorous stirring. Subsequently, the mixture is allowed to cool to 25? C. and 400 cm.sup.3 of methanol is added. The precipitate is filtered off, dried in air and purified by column chromatography using petroleum ether (b.p. 40-60? C.) and dichloromethane as eluents. The yield is 262 mg (18%).

[0374] .sup.1H NMR (400 MHz, Chloroform-d) ? 7.85 (d, J=1.4 Hz, 2H), 7.21 (d, J=1.4 Hz, 2H), 4.50 (t, J=6.7 Hz, 4H), 2.74 (m 4H), 1.86 (m, 4H), 1.71 (m, 4H), 1.55-1.25 (m, 72H), 0.86 (m, 12H).

Example M7

[0375] Monomer 7 was prepared as follows

4,8-Bis-[4-(2-octyl-dodecyl)-thiophen-2-yl]-benzo[1,2-d;4,5-d]bisthiazole-2,6-dicarboxylic acid didodecyl ester (7.1)

[0376] ##STR00086##

[0377] 4,8-Dibromo-benzo[1,2-d;4,5-d]bisthiazole-2,6-dicarboxylic acid didodecyl ester (571 mg; 0.74 mmol; 1.00 eq.), tributyl-[4-(2-octyl-dodecyl)-thiophen-2-yl]-stannane (1108 mg; 1.70 mmol; 2.30 eq.), [Pd.sub.2(dba).sub.3] (54 mg; 0.06 mmol; 0.08 eq.), tri-o-tolyl-phosphane (36 mg; 0.12 mmol; 0.16 eq.) are placed into a round bottomed flask and degassed. Toluene (6.0 cm.sup.3) is added and the reaction mixture is carefully degassed for 30 minutes. The mixture is then heated to 120? C. for 20 h under nitrogen atmosphere and vigorous stirring. Subsequently, the mixture is allowed to cool to 25? C., diluted by addition of dichloromethane (20 cm.sup.3) and precipitated by addition of methanol (400 cm.sup.3). The precipitate was filtered off and purified by column chromatography using petroleum ether (bp. 40-60? C.) and dichloromethane as eluents. The product is obtained as a dark red oil which solidifies on standing (688 mg, 69.5%).

[0378] .sup.1H NMR and .sup.1H-.sup.1H COSY NMR (400 MHz, Chloroform-d) ? 7.81 (d, J=1.4 Hz, 2H, thiophene C.sub.aromH), 7.19 (d, J=1.4 Hz, 2H, thiophene Carom-H), 4.49 (t, J=6.8 Hz, 4H, COOCH.sub.2), 2.68 (d, J=6.8 Hz, 4H, C.sub.aromCH.sub.2), 1.93-1.83 (m, 4H, COOCH.sub.2CH.sub.2), 1.71 (bs, 2H, C.sub.aromCH.sub.2CH), 1.55-1.45 (m, 4H, COOCH.sub.2CH.sub.2CH.sub.2), 1.42-1.14 (m, 76H), 0.91-0.82 (m, 18H, CH.sub.3).

4,8-Bis-[5-bromo-4-(2-octyl-dodecyl)-thiophen-2-yl]-benzo[1,2-d;4,5-d]bisthiazole-2,6-dicarboxylic acid didodecyl ester (7)

[0379] ##STR00087##

[0380] To a round-bottom flask is added 4,8-bis-[4-(2-octyl-dodecyl)-thiophen-2-yl]-benzo[1,2-d;4,5-d]bisthiazole-2,6-dicarboxylic acid didodecyl ester (688.00 mg; 0.51 mmol; 1.00 eq.), chloroform (12 cm.sup.3), acetic acid (4 cm.sup.3). The mixture is stirred at r.t. and degassed. 1-Bromo-pyrrolidine-2,5-dione (187.02 mg; 1.05 mmol; 2.05 eq.) is added in one portion and the mixture stirred for 2 hours (TLC control). The product is precipitated by addition of methanol (200 cm.sup.3) and filtered off. The crude material is then dissolved in cyclohexane and purified by column chromatography using petroleum ether (b.p. 40-60? C.) and dichloromethane as eluents and recrystallised from iso-propanol. The yield is 641 mg (83.4%).

[0381] .sup.1H NMR (400 MHz, Chloroform-d) ? 7.65 (s, 2H, thiophene C.sub.aromH), 4.54 (t, J=6.7 Hz, 4H, COOCH.sub.2), 2.65 (d, J=7.1 Hz, 4H, C.sub.aromCH.sub.2), 1.91 (m, 4H, COOCH.sub.2CH.sub.2), 1.78 (bs, 2H, C.sub.aromCH.sub.2CH), 1.62-1.50 (m, 4H, COOCH.sub.2CH.sub.2CH.sub.2), 1.49-1.17 (m, 76H), 0.94-0.81 (m, 18H).

Example P1

[0382] Polymer P1 was prepared as follows.

Poly-[2,6-(4,8-didodecyl-benzo[1,2-b;4,5-b]dithiophene)-co-4,7-(5,6-bis-octyloxy-benzo[1,2,5]thiadiazole)-co-4,8-(benzo[1,2-d;4,5-d]bisthiazole-2,6-dicarboxylic acid didodecyl ester)] (P1)

[0383] ##STR00088##

[0384] To a round bottomed flask is added 4,8-didodecyl-2,6-bis-trimethylstannanyl-benzo[1,2-b;4,5-b]dithiophene (426.27 mg; 0.50 mmol; 1.00 eq.), 4,7-dibromo-5,6-bis-octyloxy-benzo[1,2,5]thiadiazole (137.60 mg; 0.25 mmol; 0.50 eq.), 4,8-dibromo-benzo[1,2-d;4,5-d]bisthiazole-2,6-dicarboxylic acid didodecyl ester (193.68 mg; 0.25 mmol; 0.50 eq.), tris(dibenzylideneacetone)dipalladium(0) (18.3 mg; 20 ?mol; 0.04 eq.) and tri-o-tolyl-phosphine (24.4 mg; 80 ?mol; 0.16 eq.). To the vessel is added degassed chlorobenzene (6.25 cm.sup.3) and the reaction mixture is degassed further for 15 minutes. The reaction mixture is heated to 110? C. and stirred at this temperature for 1 hour. Tributyl-phenyl-stannane (734 mg; 2 mmol; 4.00 eq.) is then added followed by an additional 1 hour heating at 130? C. Next, bromo-benzene (471 mg; 3.00 mmol; 6 eq.) is added followed by an additional 1 hour heating at 130? C. After completion of the reaction, the reaction mixture is allowed to cool to 60? C. and precipitated into stirred methanol (100 cm.sup.3). The polymer is collected by filtration and washed with methanol (2?10 cm.sup.3) to give a solid. The polymer is sequentially extracted by Soxhlet extraction with acetone, petroleum ether (40-60? C.), cyclohexane, dichloromethane, chloroform and chlorobenzene. The chloroform fraction is precipitated by addition to stirred methanol (100 cm.sup.3) and collected by filtration to give a black solid (51 mg).

[0385] GPC (50? C., chlorobenzene): Mn=88.8 kg/mol, Mw=410.7 kg/mol, PDI=4.62

[0386] The chlorobenzene fraction is precipitated by addition to stirred methanol (100 cm.sup.3) and collected by filtration to give a black solid (385 mg).

[0387] GPC (50? C., chlorobenzene): Mn=103.3 kg/mol, Mw=569.4 kg/mol, PDI=5.50

Example P2

[0388] Polymer P2 was prepared as follows.

Poly-[2,6-(4,8-didodecyl-benzo[1,2-b;4,5-b]dithiophene)-co-4,8-(6-(3,7-dimethyl-octyl)-[1,2,5]thiadiazolo[3,4-e]isoindole-5,7-dione)-co-4,8-(benzo[1,2-d;4,5-d]bisthiazole-2,6-dicarboxylic acid didodecyl ester)] (P2)

[0389] ##STR00089##

[0390] To a round bottomed flask is added 4,8-didodecyl-2,6-bis-trimethylstannanyl-benzo[1,2-b;4,5-b]dithiophene (298.39 mg; 0.35 mmol; 1.00 eq.), 4,8-dibromo-benzo[1,2-d;4,5-d]bisthiazole-2,6-dicarboxylic acid didodecyl ester (203.36 mg; 0.26 mmol; 0.75 eq.), 4,8-dibromo-6-(3,7-dimethyl-octyl)-[1,2,5]thiadiazolo[3,4-e]isoindole-5,7-dione (44.03 mg; 0.09 mmol; 0.25 eq.), tri-o-tolyl-phosphine (17 mg; 56 ?mol; 0.16 eq.) and tris(dibenzylideneacetone)dipalladium(0) (12.8 mg; 14 ?mol; 0.04 eq.). To the vessel is added degassed chlorobenzene (4.4 cm.sup.3) and the reaction mixture is degassed further for 15 minutes. The reaction mixture is heated to 110? C. and stirred at this temperature for 1 hour. Tributyl-phenyl-stannane (514 mg; 1.40 mmol; 4.00 eq.) is then added followed by an additional 1 hour heating at 130? C. Next, bromobenzene (329.72 mg; 2.10 mmol; 6 eq.) is added followed by an additional 1 hour heating at 130? C. After completion of the reaction, the reaction mixture is allowed to cool to 60? C. and precipitated into stirred methanol (100 cm.sup.3). The polymer is collected by filtration and washed with methanol (2?10 cm.sup.3) to give a solid. The polymer is sequentially extracted by Soxhlet extraction with acetone, petroleum ether (40-60? C.), cyclohexane, chloroform and chlorobenzene. The cyclohexane fraction is precipitated by addition to stirred methanol (100 cm.sup.3) and collected by filtration to give a black solid (306 mg).

[0391] GPC (50? C., chlorobenzene): Mn=11.3 kg/mol, Mw=23.3 kg/mol, PDI=2.061

Example P3

[0392] Polymer P3 was prepared as follows.

Poly-[2,6-(4,8-didodecyl-benzo[1,2-b;4,5-b]dithiophene)-co-2,6-(benzo[1,2-b;4,5-b]dithiophene-4,8-dicarboxylic acid didodecyl ester)-co-4,8-(benzo[1,2-d;4,5-d]bisthiazole-2,6-dicarboxylic acid didodecyl ester)] (P3)

[0393] ##STR00090##

[0394] To a round bottomed flask is added 4,8-didodecyl-2,6-bis-trimethylstannanyl-benzo[1,2-b;4,5-b]dithiophene (255.76 mg; 0.30 mmol; 1.00 eq.), 4,8-dibromo-benzo[1,2-d;4,5-d]bisthiazole-2,6-dicarboxylic acid didodecyl ester (209.17 mg; 0.27 mmol; 0.90 eq.), 2,6-dibromo-benzo[1,2-b;4,5-b]dithiophene-4,8-dicarboxylic acid didodecyl ester (23.18 mg; 0.03 mmol; 0.10 eq.), tri-o-tolyl-phosphine (14.61 mg; 48.00 ?mol; 0.16 eq.) and tris(dibenzylideneacetone)dipalladium(0) (10.99 mg; 12.00 ?mol; 0.04 eq.) To the vessel is added degassed chlorobenzene (4.15 cm.sup.3) and the reaction mixture is degassed further for 15 minutes. The reaction mixture is heated to 110? C. and stirred at this temperature for 1 hour. Tributyl-phenyl-stannane (441 mg; 1.20 mmol; 4.00 eq.) is then added followed by an additional 1 hour heating at 130? C. Next, bromobenzene (282 mg; 1.20 mmol; 6 eq.) is added followed by an additional 1 hour heating at 130? C. After completion of the reaction, the reaction mixture is allowed to cool to 60? C. and precipitated into stirred methanol (100 cm.sup.3). The polymer is collected by filtration and washed with methanol (2?10 cm.sup.3) to give a solid. The polymer is sequentially extracted by Soxhlet extraction with acetone, petroleum ether (40-60? C.), cyclohexane, chloroform and chlorobenzene. The cyclohexane fraction is precipitated by addition to stirred methanol (100 cm.sup.3) and collected by filtration to give a black solid (304 mg).

[0395] GPC (50? C., chlorobenzene): Mn=12.3 kg/mol, Mw=25.2 kg/mol, PDI=2.04

Example P4

[0396] Polymer P4 was prepared as follows.

Poly-[2,6-(4,8-didodecyl-benzo[1,2-b;4,5-b]dithiophene)-co-2,5-bis-thieno[3,2-b]thiophene-co-4,8-(benzo[1,2-d;4,5-d]bisthiazole-2,6-dicarboxylic acid didodecyl ester)] (P4)

[0397] ##STR00091##

[0398] To a round bottomed flask is added 4,8-didodecyl-2,6-bis-trimethylstannanyl-benzo[1,2-b;4,5-b]dithiophene (131.39 mg; 0.15 mmol; 0.50 eq.) 2,5-bis-trimethylstannanyl-thieno[3,2-b]thiophene (71.80 mg; 0.15 mmol; 0.50 eq.), 4,8-dibromo-benzo[1,2-d;4,5-d]bisthiazole-2,6-dicarboxylic acid didodecyl ester (238.80 mg; 0.31 mmol; 1.00 eq.), tri-o-tolyl-phosphine (15 mg; 49 ?mol; 0.16 eq.) and tris(dibenzylideneacetone)dipalladium(0) (11 mg; 12 ?mol; 0.04 eq.). To the vessel is added degassed chlorobenzene (2.20 cm.sup.3) and the reaction mixture is degassed further for 10 minutes. The reaction mixture is heated to 110? C. and stirred at this temperature for 15 minutes. After completion of the reaction, the reaction mixture is allowed to cool to 60? C. and washed with methanol. The polymer is collected by filtration and washed with methanol (2?10 cm.sup.3) to give a solid. The polymer is sequentially extracted by Soxhlet extraction with acetone, petroleum ether (40-60? C.), cyclohexane, chloroform and chlorobenzene, but is found to be insoluble in these solvents.

Example P5

[0399] Polymer P5 was prepared as follows.

Poly-[2,6-(4,8-didodecyl-benzo[1,2-b;4,5-b]dithiophene)-co-4,8-(benzo[1,2-d;4,5-d]bisthiazole-2,6-dicarboxylic acid didodecyl ester)-co-4,8-(2,6-bis-(1-hexyl-nonyl)-benzo[1,2-d;4,5-d]bisthiazole)] (P5)

[0400] ##STR00092##

[0401] To a round bottomed flask is added 4,8-didodecyl-2,6-bis-trimethylstannanyl-benzo[1,2-b;4,5-b]dithiophene (285.44 mg; 0.33 mmol; 1.00 eq.), 4,8-dibromo-2,6-bis-(1-hexyl-nonyl)-benzo[1,2-d;4,5-d]bisthiazole (129.05 mg; 0.17 mmol; 0.50 eq.), 4,8-dibromo-benzo[1,2-d;4,5-d]bisthiazole-2,6-dicarboxylic acid didodecyl ester (129.69 mg; 0.17 mmol; 0.50 eq.), tri-o-tolyl-phosphine (16 mg; 54 ?mol; 0.16 eq.) and tris(dibenzylideneacetone)dipalladium(0) (12.26 mg; 13.39 ?mol; 0.04 eq.). To the vessel is added degassed chlorobenzene (4.2 cm.sup.3) and the reaction mixture is degassed further for 10 minutes. The reaction mixture is heated to 110? C. and stirred at this temperature for 30 minutes. After completion of the reaction, the reaction mixture is heated to 110? C. with additional 15 cm.sup.3 of chlorobenzene, cooled to 60? C. and precipitated by addition to methanol (150 cm.sup.3). The polymer is collected by filtration and washed with methanol (2?10 cm.sup.3) to give a solid. The polymer is sequentially extracted by Soxhlet extraction with acetone, petroleum ether (40-60? C.), cyclohexane, chloroform and chlorobenzene. The chloroform fraction is precipitated by addition to methanol (250 cm.sup.3) and collected by filtration to give a black solid (20 mg, 5.2%).

[0402] GPC (50? C., chlorobenzene) M.sub.n=24.0 kg mol.sup.?1; M.sub.w=94.5 kg mol.sup.?1; PDI=3.93.

Example P6

[0403] Polymer P6 was prepared as follows.

Poly-[4,8-(benzo[1,2-d;4,5-d]bisthiazole-2,6-dicarboxylic acid didodecyl ester)-co-4,8-(2,6-bis-(1-hexyl-nonyl)-benzo[1,2-d;4,5-d]bisthiazole)-co-2,5-bis-thiophene] (P6)

[0404] ##STR00093##

[0405] To a round bottomed flask is added 2,5-bis-trimethylstannanyl-thiophene (140.00 mg; 0.34 mmol; 1.00 eq.), 4,8-dibromo-benzo[1,2-d;4,5-d]bisthiazole-2,6-dicarboxylic acid didodecyl ester (132.35 mg; 0.17 mmol; 0.50 eq.), 4,8-dibromo-2,6-bis-(1-hexyl-nonyl)-benzo[1,2-d;4,5-d]bisthiazole (131.69 mg; 0.17 mmol; 0.50 eq.), tris(dibenzylideneacetone)dipalladium(0) (12 mg; 14 ?mol; 0.04 eq.) and tri-o-tolyl-phosphine (17 mg; 55 ?mol; 0.16 eq.). To the vessel is added degassed chlorobenzene (4.3 cm.sup.3) and the reaction mixture is degassed further for 15 minutes. The reaction mixture is heated to 110? C. and stirred at this temperature for 1 hour. Tributyl-phenyl-stannane (501.79 mg; 1.37 mmol; 4.00 eq.) is then added followed by an additional 1 hour heating at 110? C. Next, bromobenzene (321.87 mg; 2.05 mmol; 6.00 eq.) is added followed by an additional 1 hour heating at 110? C. After completion of the reaction, the reaction mixture is allowed to cool to 60? C. and precipitated into methanol (100 cm.sup.3). The polymer is sequentially extracted by Soxhlet extraction with acetone, petroleum ether (40-60? C.), cyclohexane, chloroform and chlorobenzene. The chloroform fraction is precipitated by addition to methanol (250 cm.sup.3) and collected by filtration to give a dark blue solid (197.00 mg; 0.14 mmol; 82.9%).

[0406] GPC (50? C., chlorobenzene) M.sub.n=32.6 kg mol.sup.?1; M.sub.w=135.2 kg mol.sup.?1; PDI=4.14.

Example P7

[0407] Polymer P7 was prepared as follows.

Poly-[4,8-(2,6-bis-(1-hexyl-nonyl)-benzo[1,2-d;4,5-d]bisthiazole)-co-2,5-bis-thiophene-co-5-thiophen-2-yl-(4,8-bis-6-(2-octyl-dodecyl)-[1,2,5]thiadiazolo[3,4-e]isoindole-5,7-dione] (P7)

[0408] ##STR00094##

[0409] To a round bottomed flask is added 2,5-bis-trimethylstannanyl-thiophene (149.54 mg; 0.36 mmol; 2.00 eq.), 4,8-bis-(5-bromo-thiophen-2-yl)-6-(2-octyl-dodecyl)-[1,2,5]thiadiazolo[3,4-e]isoindole-5,7-dione (147.40 mg; 0.18 mmol; 1.00 eq.), 4,8-dibromo-2,6-bis-(1-hexyl-nonyl)-benzo[1,2-d;4,5-d]bisthiazole (140.66 mg; 0.18 mmol; 1.00 eq.), tris(dibenzylideneacetone)dipalladium(0) (6.68 mg; 7.30 ?mol; 0.04 eq.) and tri-o-tolyl-phosphine (8.89 mg; 29.20 ?mol; 0.16 eq.). To the vessel is added degassed chlorobenzene (5.00 cm.sup.3) and the reaction mixture is degassed further for 15 minutes. The reaction mixture is heated to 110? C. and stirred at this temperature for 30 minutes. Tributyl-phenyl-stannane (0.3 cm.sup.3) is then added followed by an additional 1 hour heating at 110? C. Next, bromobenzene (0.2 cm.sup.3) is added followed by an additional 1 hour heating at 110? C. After completion of the reaction, the reaction mixture is allowed to cool to 60? C. and precipitated into methanol (100 cm.sup.3). The material is sequentially extracted by Soxhlet extraction with acetone and petroleum ether (40-60? C.), cyclohexane, chloroform and chlorobenzene. The cyclohexane fraction is precipitated by addition to methanol (250 cm.sup.3) and collected by filtration to give a dark solid (98 mg).

[0410] GPC (50? C., chlorobenzene) M.sub.n=21.4 kg mol.sup.?1; M.sub.w=41.1 kg mol.sup.?1; PDI=1.92.

[0411] The chloroform fraction is precipitated by addition to methanol (250 cm.sup.3) and collected by filtration to give a dark solid (116 mg).

[0412] GPC (50? C., chlorobenzene) M.sub.n=28.6 kg mol.sup.?1; M.sub.w=64.7 kg mol.sup.?1; PDI=2.26.

Example P8

[0413] Polymer P8 was prepared as follows

##STR00095##

[0414] To a round bottomed flask is added 4,8-didodecyl-2,6-bis-trimethylstannanyl-benzo[1,2-b;4,5-b]dithiophene (426.27 mg; 0.50 mmol; 1.00 eq.), 4,8-dibromo-benzo[1,2-d;4,5-d]bisthiazole-2,6-dicarboxylic acid dihexadecyl ester (221.73 mg; 0.25 mmol; 0.50 eq.), 4,8-dibromo-benzo[1,2-d;4,5-d]bisthiazole-2,6-dicarboxylic acid didodecyl ester (193.68 mg; 0.25 mmol; 0.50 eq.), Pd2(dba)3 (18.31 mg; 20.00 ?mol; 0.04 eq.) and tri-o-tolyl-phosphine (24.35 mg; 80.00 ?mol; 0.16 eq.). To the vessel is added degassed chlorobenzene (6.25 cm.sup.3) and the reaction mixture is degassed further for 15 minutes. The reaction mixture is heated to 110? C. and stirred at this temperature for 1 hours. Tributyl-phenyl-stannane (734.31 mg; 2.00 mmol; 4.00 eq.) is then added followed by an additional 1 hour heating at 130? C. Next, bromo-benzene (471.02 mg; 3.00 mmol; 6.00 eq.) is added followed by an additional 1 hour heating at 130? C. After completion of the reaction, the reaction mixture is allowed to cool to 60? C. and precipitated into stirred methanol (100 cm.sup.3). The polymer is collected by filtration and washed with methanol (2?10 cm.sup.3) to give a solid. The polymer is sequentially extracted by Soxhlet extraction with acetone, petroleum ether (40-60? C.), cyclohexane and chloroform. The cyclohexane fraction is precipitated by addition to methanol (100 cm.sup.3) and collected by filtration to give a black solid (556.00 mg; 93.0%).

[0415] GPC (50? C., chlorobenzene): Mn=43.6 kg/mol, Mw=190.4 kg/mol, PDI=4.362

Example P9

[0416] Polymer P9 was prepared as follows

##STR00096##

[0417] To a round bottomed flask is added 5,5-bis-trimethylstannanyl-[2,2]bithiophenyl (140.00 mg; 0.28 mmol; 1.00 eq.), 4,8-bis-[5-bromo-4-(2-octyl-dodecyl)-thiophen-2-yl]-benzo[1,2-d;4,5-d]bisthiazole-2,6-dicarboxylic acid didodecyl ester (426.94 mg; 0.28 mmol; 1.00 eq.), tri-o-tolyl-phosphine (13.86 mg; 45.54 ?mol; 0.16 eq.) and Pd2(dba)3 (10.43 mg; 11.38 ?mol; 0.04 eq.). To the vessel is added degassed chlorobenzene (3.56 cm.sup.2) and the reaction mixture is degassed further for 10 minutes. The reaction mixture is heated to 110? C. and stirred at this temperature for 60 minutes.

[0418] Tributyl-phenyl-stannane (0.3 cm.sup.3) is then added followed by an additional 1 hour heating at 110? C. Next, bromo-benzene (0.5 cm.sup.3) is added followed by an additional overnight heating at 110? C.

[0419] After completion of the reaction, the reaction mixture is transferred to a flask containing 150 cm.sup.3 methanol. The polymer is collected by filtration and washed with methanol (2?10 cm.sup.3) to give a solid. The polymer is sequentially extracted by Soxhlet extraction with acetone, petroleum ether (40-60? C.), cyclohexane and chloroform. The cyclohexane fraction is precipitated by addition to methanol (250 cm.sup.3) and collected by filtration to give a black solid: (69.80 mg; 16.9%).

[0420] GPC (50? C., chlorobenzene) M.sub.n=48.8 kg mol.sup.?1; M.sub.w=239.2 kg mol.sup.?1; PDI=4.9

Example P10

[0421] Polymer P10 was prepared as follows

##STR00097##

[0422] To a round bottomed flask is added 5,5-bis-trimethylstannanyl-[2,2]bithiophenyl (140.00 mg; 0.28 mmol; 1.00 eq.), 4,8-bis-[5-bromo-4-(2-octyl-dodecyl)-thiophen-2-yl]-benzo[1,2-d;4,5-d]bisthiazole-2,6-dicarboxylic acid didodecyl ester (207.50 mg; 0.14 mmol; 1.00 eq.), tri-o-tolyl-phosphine (6.74 mg; 22.13 ?mol; 0.16 eq.) and Pd2(dba)3 (5.07 mg; 5.53 ?mol; 0.04 eq.). To the vessel is added degassed chlorobenzene (1.71 cm.sup.3) and the reaction mixture is degassed further for 10 minutes.

[0423] The reaction mixture is heated to 110? C. and stirred at this temperature for 60 minutes. Tributyl-phenyl-stannane (0.3 cm.sup.3) is then added followed by an additional 1 hour heating at 110? C. Next, bromo-benzene (0.5 cm.sup.3) is added followed by an additional overnight heating at 110? C.

[0424] After completion of the reaction, the reaction mixture is transferred to a flask containing 150 cm.sup.3 methanol. The polymer is collected by filtration and washed with methanol (2?10 cm.sup.3) to give a solid. The polymer is sequentially extracted by Soxhlet extraction with acetone, petroleum ether (40-60? C.), cyclohexane and chloroform and chlorobenzene. The chlorobenzene fraction is precipitated by addition to methanol (250 cm.sup.3) and collected by filtration to give a black solid (27.00 mg; 13.7%)

[0425] GPC (50? C., chlorobenzene) M.sub.n=51.4 kg mol.sup.?1; M.sub.w=252.6 kg mol.sup.?1; PDI=4.91.

B) USE EXAMPLES

Bulk Heterojunction OPV Devices for Polymers P1-P3 and P5-P9

[0426] Organic photovoltaic (OPV) devices are fabricated on pre-patterned ITO-glass substrates (13?/sq.) purchased from LUMTEC Corporation. Substrates were cleaned using common solvents (acetone, iso-propanol, deionized-water) in an ultrasonic bath. A conducting polymer poly(ethylene dioxythiophene) doped with poly(styrene sulfonic acid) [Clevios VPAI 4083 (H. C. Starck)] is mixed in a 1:1 ratio with deionized-water. This solution was filtered using a 0.45 ?m filter before spin-coating to achieve a thickness of 20 nm. Substrates were exposed to ozone prior to the spin-coating process to ensure good wetting properties. Films were then annealed at 140? C. for 30 minutes in a nitrogen atmosphere where they were kept for the remainder of the process. Active material solutions (i.e. polymer+PCBM) were prepared and stirred overnight to fully dissolve the solutes. Thin films were either spin-coated or blade-coated in a nitrogen atmosphere to achieve active layer thicknesses between 100 and 500 nm as measured using a profilometer. A short drying period followed to ensure removal of any residual solvent.

[0427] Typically, spin-coated films were dried at 23? C. for 10 minutes and blade-coated films were dried at 70? C. for 2 minutes on a hotplate. For the last step of the device fabrication, Ca (30 nm)/Al (125 nm) cathodes were thermally evaporated through a shadow mask to define the cells. Current-voltage characteristics were measured using a Keithley 2400 SMU while the solar cells were illuminated by a Newport Solar Simulator at 100 mW.Math.cm?2 white light. The Solar Simulator was equipped with AM1.5G filters. The illumination intensity was calibrated using a Si photodiode. All the device preparation and characterization is done in a dry-nitrogen atmosphere.

[0428] Power conversion efficiency is calculated using the following equation

[00001]$?=\frac{V_{\mathrm{oc}}?J_{\mathrm{sc}}?\mathrm{FF}}{P_{\mathrm{in}}}$

[0429] where FF is defined as

[00002]$\mathrm{FF}=\frac{V_{\max }?J_{\max }}{V_{\mathrm{oc}}?J_{\mathrm{sc}}}$

[0430] OPV devices were prepared wherein the photoactive layer contains a blend of a polymer selected from one of the Examples P1-P3 and P5-P9 with the fullerene PC.sub.60BM, which is coated from a solution in a solvent and at a total solid concentration as shown in Table 2 below. The OPV device characteristics are shown in Table 2.

TABLE-US-00001 TABLE 2 Photovoltaic cell characteristics. Polymer Solvent Voc/(mV) Jsc/(mA/cm.sup.2) FF/% PCE/% P1 DMA/DIO 835 8.2 40 2.8 P2 o-xylene/DMA 837 0.6 43 0.2 P3 DMA/DIO 823 2.0 43 0.7 P5 ODCB 800 1.0 31 0.3 P6 ODCB 704 3.6 33 0.8 P7 DMA/DIO 677 2.3 29 0.5 P8 DMA/DIO 824 2.0 51 0.8 P9 ODCB 826 1.2 33 0.3

[0431] The device data above shows that incorporation of the BBT unit into polymers does yield materials which can be used in OPV devices. The materials show high Vocs, which demonstrates that they have the potential to achieve high performances in OPV devices.