Quinolinium dyes with fluorinated counter anion for dye sensitized solar cells

Abstract

The present invention relates to an electrode layer comprising a porous film made of oxide semiconductor fine particles sensitized with a quinolinium dye having a fluorinated counteranion. Moreover the present invention relates to a photoelectric conversion device comprising said electrode layer, a dye sensitized solar cell comprising said photoelectric conversion device and to novel quinolinium dyes having a fluorinated counteranion.

Claims

1. An electrode layer comprising a porous film which comprises oxide semiconductor fine particles sensitized with a dye of formula (I), ##STR00143## where n is 1, 2, 3, 4, 5 or 6; R.sup.1 and R.sup.2 are independently of each other selected from the group consisting of hydrogen, C.sub.1-C.sub.20-alkyl wherein alkyl is uninterrupted or interrupted by O, S, CO, NR.sup.14 or combinations thereof, C.sub.6-C.sub.20-aryl, heteroaryl and C.sub.6-C.sub.20-aryl which has 1, 2 or 3 substituents selected from C.sub.1-C.sub.8-alkyl, and R.sup.1 can additionally be a radical of formula D; D is independently selected from a radical of formulae D.1 and D.2 ##STR00144## where * denotes the bond to the remaining compound of formula I, R.sup.17 and R.sup.18 are independently of each other selected from unsubstituted or substituted C.sub.1-C.sub.20-alkyl, unsubstituted or substituted C.sub.2-C.sub.20-alkenyl, unsubstituted or substituted C.sub.2-C.sub.20-alkynyl, unsubstituted or substituted C.sub.7-C.sub.20-aralkyl, unsubstituted or substituted C.sub.8-C.sub.20-aralkenyl, unsubstituted or substituted C.sub.8-C.sub.20-aralkynyl, unsubstituted or substituted C.sub.6-C.sub.20-aryl, unsubstituted or substituted heteroaryl, unsubstituted or substituted heterocyclyl, unsubstituted or substituted C.sub.4-C.sub.20-cycloalkyl, unsubstituted or substituted C.sub.5-C.sub.20-cycloalkenyl and unsubstituted or substituted C.sub.6-C.sub.20-cycloalkynyl, wherein alkyl, alkenyl, alkynyl or the aliphatic moieties in aralkyl, aralkenyl or aralkynyl are uninterrupted or interrupted by O, S, CO, NR.sup.14 or combinations thereof, where R.sup.14 is hydrogen, C.sub.1-C.sub.20-alkyl or C.sub.6-C.sub.10-aryl; or R.sup.17 and R.sup.18 form together with the nitrogen atom to which they are attached an unsubstituted or substituted 5-, 6- or 7-membered ring; or R.sup.17 and R.sup.20 form together with the nitrogen atom to which R.sup.17 is attached and the carbon atoms of the benzene ring to which R.sup.20 and NR.sup.17 are attached an unsubstituted or substituted 5-, 6- or 7-membered ring; or R.sup.17 and R.sup.22 form together with the nitrogen atom to which R.sup.17 is attached and the carbon atoms of the benzene ring to which R.sup.22 and NR.sup.17 are attached an unsubstituted or substituted 5-, 6- or 7-membered ring; and/or R.sup.18 and R.sup.19 form with the nitrogen atom to which R.sup.18 is attached and the carbon atoms of the benzene ring to which R.sup.19 and NR.sup.18 are attached an unsubstituted or substituted 5-, 6- or 7-membered ring; R.sup.15, R.sup.16, R.sup.19, R.sup.20, R.sup.21, R.sup.22, R.sup.23 and R.sup.24 are independently of each other selected from the group consisting of hydrogen, NR.sup.25R.sup.26, OR.sup.25, SR.sup.25, NR.sup.25NR.sup.26R.sup.27, NR.sup.25OR.sup.26, OCOR.sup.25, OCOOR.sup.25, OCONR.sup.25R.sup.26, NR.sup.25COR.sup.26, NR.sup.25COOR.sup.26, NR.sup.25CONR.sup.26R.sup.27, COR.sup.25, COOR.sup.25, CONR.sup.25R.sup.26, SCOR.sup.25, COSR.sup.25, CONR.sup.25NR.sup.26R.sup.27, CONR.sup.25OR.sup.26, COOCOR.sup.25, COOCOOR.sup.25, COOCONR.sup.25R.sup.26, CONR.sup.25COR.sup.26, CONR.sup.25COOR.sup.26, unsubstituted or substituted C.sub.1-C.sub.20-alkyl, unsubstituted or substituted C.sub.2-C.sub.20-alkenyl, unsubstituted or substituted C.sub.2-C.sub.20-alkynyl, unsubstituted or substituted C.sub.7-C.sub.20-aralkyl, unsubstituted or substituted C.sub.8-C.sub.20-aralkenyl, unsubstituted or substituted C.sub.8-C.sub.20-aralkynyl, unsubstituted or substituted C.sub.6-C.sub.20-aryl, unsubstituted or substituted heteroaryl, unsubstituted or substituted heterocyclyl, unsubstituted or substituted C.sub.4-C.sub.20-cycloalkyl, unsubstituted or substituted C.sub.5-C.sub.20-cycloalkenyl and unsubstituted or substituted C.sub.6-C.sub.20-cycloalkynyl, wherein alkyl, alkenyl, alkynyl or the aliphatic moieties in aralkyl, aralkenyl or aralkynyl are uninterrupted or interrupted by O, S, CO, NR.sup.14 or combinations thereof; R.sup.25, R.sup.26 and R.sup.27 are independently of each other selected from hydrogen, unsubstituted or substituted C.sub.1-C.sub.20-alkyl, unsubstituted or substituted C.sub.2-C.sub.20-alkenyl, unsubstituted or substituted C.sub.2-C.sub.20-alkynyl, unsubstituted or substituted C.sub.7-C.sub.20-aralkyl, unsubstituted or substituted C.sub.8-C.sub.20-aralkenyl, unsubstituted or substituted C.sub.8-C.sub.20-aralkynyl, unsubstituted or substituted C.sub.6-C.sub.20-aryl, unsubstituted or substituted heteroaryl, unsubstituted or substituted heterocyclyl, unsubstituted or substituted C.sub.4-C.sub.20-cycloalkyl, unsubstituted or substituted C.sub.5-C.sub.20-cycloalkenyl and unsubstituted or substituted C.sub.6-C.sub.20-cycloalkynyl, wherein alkyl, alkenyl, alkynyl or the aliphatic moieties in aralkyl, aralkenyl or aralkynyl are uninterrupted or interrupted by O, S, CO, NR.sup.14 or combinations thereof; A is a radical of formulae A.1, A.2, A.3, A.4 or A.5 ##STR00145## where # denotes the bond to the remaining compound of formula I R.sup.29, R.sup.30, R.sup.31, R.sup.32, R.sup.33, R.sup.34 and R.sup.35 are independently of each other selected from the group consisting of a radical G, hydrogen, halogen, OR.sup.36, unsubstituted or substituted unsubstituted or substituted C.sub.1-C.sub.20-alkyl, unsubstituted or substituted C.sub.2-C.sub.20-alkenyl, unsubstituted or substituted C.sub.2-C.sub.20-alkynyl, unsubstituted or substituted C.sub.7-C.sub.20-aralkyl, unsubstituted or substituted C.sub.8-C.sub.20-aralkenyl, unsubstituted or substituted C.sub.8-C.sub.20-aralkynyl, unsubstituted or substituted C.sub.6-C.sub.20-aryl, unsubstituted or substituted heteroaryl, unsubstituted or substituted heterocyclyl, unsubstituted or substituted C.sub.5-C.sub.20-cycloalkyl, unsubstituted or substituted C.sub.5-C.sub.20-cycloalkenyl and unsubstituted or substituted C.sub.6-C.sub.20-cycloalkynyl, wherein alkyl, alkenyl, alkynyl or the aliphatic moieties in aralkyl, aralkenyl or aralkynyl are uninterrupted or interrupted by O, S, CO, NR.sup.14 or combinations thereof; with the proviso that at least one of the radicals R.sup.29, R.sup.30, R.sup.31, R.sup.32, R.sup.33, R.sup.34 and R.sup.35 is a radical G, where R.sup.36 is unsubstituted or substituted C.sub.1-C.sub.20-alkyl, unsubstituted or substituted C.sub.6-C.sub.20-aryl, unsubstituted or substituted heteroaryl, wherein alkyl is uninterrupted or interrupted by O, S, CO, NR.sup.14 or combinations thereof; G is selected from the group consisting of R.sup.28COOH, R.sup.28COO.sup.Z.sup.+, R.sup.28CO(CO)OH, R.sup.28CO(CO)O.sup.Z.sup.+, R.sup.28S(O).sub.2OH, R.sup.28S(O).sub.2O.sup.Z.sup.+, R.sup.2OS(O).sub.2OH, R.sup.28OS(O).sub.2O.sup.Z.sup.+, R.sup.28P(O)(OH).sub.2, R.sup.28P(O)(O.sup.Z.sup.+).sub.2, R.sup.28P(O)(OH)(O.sup.Z.sup.+), R.sup.28OP(O)(OH).sub.2, R.sup.28OP(O)(O.sup.Z.sup.+).sub.2, R.sup.28OP(O)(OH)(O.sup.Z.sup.+), R.sup.28CONHOH, R.sup.28S(O).sub.2NHOH, R.sup.28NR.sup.14S(O).sub.2OH and R.sup.28NR.sup.14S(O).sub.2O.sup.Z.sup.+; where R.sup.28 is a direct bond, C.sub.1-C.sub.20-alkylene, C.sub.2-C.sub.4-alkenylene or C.sub.6-C.sub.10-arylene; Z.sup.+ is an organic or inorganic cation equivalent; Y.sup. is a fluorinated organic anion selected from Y.1, Y.2, Y.3, Y.4, Y.5 and Y.6; ##STR00146## wherein X.sup. is S(O).sub.2O.sup., OS(O).sub.2O.sup., COO.sup., ##STR00147## Rf.sup.1 is selected from the group consisting of halogen, unsubstituted or substituted C.sub.1-C.sub.20-alkyl, unsubstituted or substituted haloalkyl, unsubstituted or substituted C.sub.2-C.sub.20-alkenyl, unsubstituted or substituted haloalkenyl, unsubstituted or substituted C.sub.2-C.sub.20-alkynyl, unsubstituted or substituted haloalkynyl, unsubstituted or substituted C.sub.7-C.sub.20-aralkyl, unsubstituted or substituted C.sub.8-C.sub.20-aralkenyl, unsubstituted or substituted C.sub.8-C.sub.20-aralkynyl, unsubstituted or substituted C.sub.6-C.sub.20-aryl, unsubstituted or substituted heteroaryl, unsubstituted or substituted heterocyclyl, unsubstituted or substituted C.sub.4-C.sub.20-cycloalkyl, unsubstituted or substituted C.sub.5-C.sub.20-cycloalkenyl and unsubstituted or substituted C.sub.6-C.sub.20-cycloalkynyl, wherein alkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl or the aliphatic moieties in aralkyl, aralkenyl or aralkynyl are uninterrupted or interrupted by O, S, CO, NR.sup.14 or combinations thereof, Rf.sup.2, Rf.sup.3, Rf.sup.4, Rf.sup.5 and Rf.sup.6 are independently selected from the group consisting of halogen, hydrogen, NR.sup.25R.sup.26, OR.sup.25, SR.sup.25, NR.sup.25NR.sup.26R.sup.27, NR.sup.25OR.sup.26, OCOR.sup.25, OCOOR.sup.25, OCONR.sup.25R.sup.26, NR.sup.25COR.sup.26, NR.sup.25COOR.sup.26, NR.sup.25CONR.sup.26R.sup.27, COR.sup.25, COOR.sup.25, CONR.sup.25R.sup.26, SCOR.sup.25, COSR.sup.25, CONR.sup.25NR.sup.26R.sup.27, CONR.sup.25OR.sup.26, COOCOR.sup.25, COOCOOR.sup.25, COOCONR.sup.25R.sup.26, CONR.sup.25COR.sup.26, CONR.sup.25COOR.sup.26, unsubstituted or substituted C.sub.1-C.sub.20-alkyl, unsubstituted or substituted C.sub.2-C.sub.20-alkenyl, unsubstituted or substituted C.sub.2-C.sub.20-alkynyl, unsubstituted or substituted C.sub.6-C.sub.20 aryl, unsubstituted or substituted heteroaryl, unsubstituted or substituted heterocyclyl, unsubstituted or substituted C.sub.7-C.sub.20-aralkyl, unsubstituted or substituted C.sub.8-C.sub.20-aralkenyl, unsubstituted or substituted C.sub.8-C.sub.20-aralkynyl, unsubstituted or substituted C.sub.4-C.sub.20-cycloalkyl, unsubstituted or substituted C.sub.5-C.sub.20-cycloalkenyl and unsubstituted or substituted C.sub.6-C.sub.20-cycloalkynyl, wherein alkyl, alkenyl, alkynyl or the aliphatic moieties in aralkyl, aralkenyl or aralkynyl are uninterrupted or interrupted by O, S, CO, NR.sup.14 or combinations thereof; with the proviso that at least one of the radicals Rf.sup.2, Rf.sup.3, Rf.sup.4, Rf.sup.5 and Rf.sup.6 is fluorine or C.sub.1-C.sub.20-fluoroalkyl, wherein fluoroalkyl is uninterrupted or interrupted by O, S, NR.sup.14, CO, or combinations thereof; X.sup.1, X.sup.2 and X.sup.3 are independently of each other selected from S(O).sub.2 and CO; Rf.sup.7, Rf.sup.7*, Rf.sup.8, Rr.sup.8* and Rf.sup.9 are independently of each other selected from the group consisting of unsubstituted or substituted C.sub.1-C.sub.20-fluoroalkyl, C.sub.6-C.sub.20-fluoroaryl, wherein fluoroalkyl is uninterrupted or interrupted by O, S, NR.sup.14, CO, or combinations thereof; or Rf.sup.7 and Rf.sup.8 together are C.sub.3-C.sub.6-fluoroalkyl; Rf.sup.10, Rf.sup.11, Rf.sup.12 and Rf.sup.13 are independently of each other selected from fluorine, C.sub.1-C.sub.20-fluoroalkyl and C.sub.6-C.sub.20-fluoroaryl; Rf.sup.14 and Rf.sup.15 together are C.sub.3-C.sub.7-fluoroalkyl which is unsubstituted or substituted by C.sub.1-C.sub.6-fluoroalkyl; Rg is unsubstituted or substituted C.sub.1-C.sub.20-alkyl, unsubstituted or substituted C.sub.1-C.sub.20-alkoxy, unsubstituted or substituted C.sub.6-C.sub.20-aryl or unsubstituted or substituted C.sub.6-C.sub.20aryl-O, wherein alkyl and the alkyl moiety in alkoxy is uninterrupted or interrupted by O, S, NR.sup.14, CO, or combinations thereof; wherein Y.sup. is not BF4.sup., with the proviso that if R.sup.17 and R.sup.18 are both unsubstituted or substituted fluorene, Y.sup. is not bistrifluoromethylsulfonimide, C(SO.sub.2CF.sub.3).sub.3.sup., and with the proviso that if A is a radical of the formula A.1.1c ##STR00148## Y.sup. is not (C.sub.nF.sub.2n+1SO.sub.2).sub.2N.sup., where n is an integer from 1 to 18.

2. The electrode layer according to claim 1, wherein in the radical of the formulae D.1 and D.2, R.sup.17 and R.sup.18 are independently selected from the group consisting of C.sub.1-C.sub.20-alkyl, C.sub.2-C.sub.20-alkenyl, C.sub.2-C.sub.20-alkynyl, C.sub.6-C.sub.20-aryl, heteroaryl, heterocyclyl, C.sub.7-C.sub.20-aralkyl, C.sub.8-C.sub.20-aralkenyl, C.sub.8-C.sub.20-aralkynyl, C.sub.4-C.sub.20-cycloalkyl, C.sub.5-C.sub.20-cycloalkenyl, and C.sub.6-C.sub.20-cycloalkynyl, wherein alkyl, alkenyl, alkynyl or the aliphatic moieties in aralkyl, aralkenyl or aralkynyl are uninterrupted or interrupted by O, S, NR.sup.14 or combinations thereof and/or optionally has one or more substituents selected fromthe group consisting of C.sub.4-C.sub.20-cycloalkyl, C.sub.5-C.sub.20-cycloalkenyl, C.sub.6-C.sub.20-cycloalkynyl, heterocyclyl, halogen, SR.sup.25, OR.sup.25, COOR.sup.25, OCOR.sup.25, NR.sup.25R.sup.26, CONR.sup.25R.sup.26, NR.sup.25COR.sup.26, S(O).sub.2OR.sup.25 and S(O).sub.2O.sup.Z.sup.+ and wherein aryl, the aryl moiety of aralkyl, aralkenyl, or aralkynyl, heteroaryl, heterocyclyl, cycloalkyl, cycloalkenyl or cycloalkynyl are unsubstituted or may carry one or more substituents selected from halogen, SR.sup.25, OR.sup.25, COOR.sup.25, OCOR.sup.25, NR.sup.25R.sup.26, CONR.sup.25R.sup.26, NR.sup.25COR.sup.26, S(O).sub.2OR.sup.25, S(O).sub.2O.sup.Z.sup.+, C.sub.1-C.sub.20-alkyl, C.sub.2-C.sub.20-alkenyl, C.sub.2-C.sub.20-alkynyl, C.sub.7-C.sub.20-aralkyl, C.sub.8-C.sub.20-aralkenyl, C.sub.8-C.sub.20-aralkynyl, C.sub.4-C.sub.20-cycloalkyl, C.sub.5-C.sub.20-cycloalkenyl, C.sub.6-C.sub.20-cycloalkynyl, heterocyclyl, C.sub.6-C.sub.20-aryl, C.sub.6-C.sub.20-aryl which carries one or more substituents selected from C.sub.1-C.sub.20-alkyl and OR.sup.25, maleic anhydridyl and maleimidyl, wherein the maleic anhydridyl and maleimidyl radicals are unsubstituted or optionally have substituents selectedfrom C.sub.1-C.sub.20-alkyl, C.sub.6-C.sub.20-aryl and phenyl-NR.sup.25R.sup.26; or R.sup.17 and R.sup.18 may form together with the nitrogen atom to which they are attached a 5-, 6- or 7-membered, saturated or unsaturated heterocycle which may have 1 or 2 further heteroatoms selected from O, S and N as ring members and wherein the heterocycle is unsubstituted or optionally has one or more substituents R.sup.x1, where each R.sup.x1 is selected from C.sub.1-C.sub.20-alkyl which is unsubstituted or optionally has one or more substituents R.sup.x2 and phenyl, which is unsubstituted or may carry one or more substituents R.sup.x3, in addition two radicals R.sup.x1 bonded to adjacent carbon atoms may form together with the carbon atoms to which they are bonded a 4-, 5-, 6- or 7-membered saturated or unsaturated carbocyclicring or an aromatic ring selected from benzene, naphthalene, anthracene and9H-fluorene, where the carbocyclic and the aromatic ring are unsubstituted or carry one or more substituents R.sup.x3, and/or two radicals R.sup.x1 present on the same carbon atom may be C.sub.1-C.sub.20-alkylidene which is unsubstituted or carry one or more substituents R.sup.x2, where R.sup.x2 is selected from the group consisting of halogen, SR.sup.25, OR.sup.25, COOR.sup.25, OCOR.sup.25, NR.sup.25R.sup.26, CONR.sup.25R.sup.26, NR.sup.25COR.sup.26, S(O).sub.2OR.sup.25 and S(O).sub.2O.sup.Z.sup.+, R.sup.x3 is selected from the group consisting of C.sub.1-C.sub.10-alkyl, halogen, fluoren-9-ylidenemethyl, SR.sup.25, OR.sup.25, COOR.sup.25, OCOR.sup.25, NR.sup.25R.sup.26, CONR.sup.25R.sup.26, NR.sup.25COR.sup.26, S(O).sub.2OR.sup.25 and S(O).sub.2O.sup.Z.sup.+; or R.sup.17 and R.sup.22 may form together with the nitrogen atom to which R.sup.17 is attached and the carbon atoms of the benzene ring to which R.sup.20 and NR.sup.17 are attached an unsubstituted or substituted 5-, 6- or 7-membered ring which may have 1 or 2 further heteroatoms selected from O, S and N as ring members and wherein the heterocycle is unsubstituted or may carry one or more substituents R.sup.x4; or R.sup.17 and R.sup.22 may form together with the nitrogen atom to which R.sup.17 is attached and the carbon atoms of the benzene ring to which R.sup.22 and NR.sup.17 are attached an unsubstituted or substituted 5-, 6- or 7-membered ring, which may have 1 or 2 further heteroatoms selected from O, S and N as ring members and wherein the heterocycle is unsubstituted or may carry one or more substituents R.sup.x4; and/or R.sup.18 and R.sup.19 may form with the nitrogen atom to which R.sup.18 is attached and the carbon atoms of the benzene ring to which R.sup.19 and NR.sup.18 are attached an unsubstituted or substituted 5-, 6- or 7-membered ring which may have 1 or 2 further heteroatoms selected from O, S and N as ring members and wherein the heterocycle is unsubstituted or may carry one or more substituents R.sup.x4; where each R.sup.x4 is selected from C.sub.1-C.sub.20-alkyl which is unsubstituted or may carry one or more substituents R.sup.x5 and phenyl, which is unsubstituted or carry one or more substituents R.sup.x6, in addition two radicals R.sup.x4 bonded to adjacent carbon atoms may form together with the carbon atoms to which they are bonded a 4-, 5-, 6- or 7-membered saturated or unsaturated carbocyclic ring or an aromatic ring selected from benzene, naphthalene, anthracene and 9H-fluorene, where the carbocyclic or the aromatic ring are unsubstituted or may carry one or more substituents R.sup.x6, and/or two radicals R.sup.x4 present on the same C atom may be C.sub.1-C.sub.20-alkylidene which is unsubstituted or carry one or more substituents R.sup.x5; where each R.sup.x5 has one of the meanings given for R.sup.x2, and each R.sup.x6 has one of the meaning given for R.sup.x3 and where in addition, two radicals R.sup.x6 bonded to adjacent carbon atoms may form together with the carbon atoms to which they are bonded a benzene or naphthalene ring; R.sup.15, R.sup.16, R.sup.19, R.sup.20, R.sup.21, R.sup.22, R.sup.23 and R.sup.24 are independently selected from the group consisting of hydrogen, NR.sup.25R.sup.26, OR.sup.25, SR.sup.25, NR.sup.25NR.sup.26R.sup.27, NR.sup.25OR.sup.26, OCOR.sup.25, OCOOR.sup.25, OCONR.sup.25R.sup.26, NR.sup.25COR.sup.26, NR.sup.25COOR.sup.26, NR.sup.25CONR.sup.26R.sup.27, COR.sup.25, COOR.sup.25, CONR.sup.25R.sup.26, COSR.sup.25, CONR.sup.25NR.sup.26R.sup.27, CONR.sup.25OR.sup.26, COOCOR.sup.25, COOCOOR.sup.25, COOCONR.sup.25R.sup.26, CONR.sup.25COR.sup.26, CONR.sup.25COOR.sup.26, C.sub.1-C.sub.20-alkyl, C.sub.2-C.sub.20-alkenyl, C.sub.2-C.sub.20-alkynyl, C.sub.6-C.sub.20-aryl, heteroaryl, heterocyclyl, C.sub.7-C.sub.20-aralkyl, C.sub.8-C.sub.20-aralkenyl, C.sub.8-C.sub.20-aralkynyl, C.sub.4-C.sub.20-cycloalkyl, C.sub.5-C.sub.20-cycloalkenyl and C.sub.6-C.sub.20cycloalkynyl, wherein alkyl is uninterrupted or interrupted by O, S, NR.sup.14 or combinations thereof, and wherein alkyl, the alkyl moiety of aralkyl, alkenyl, the alkenyl moiety of aralkenyl, alkynyl and the alkynyl moiety of aralkynyl may carry substituents selected from the group consisting of C.sub.4-C.sub.20-cycloalkyl, halogen, SR.sup.14, OR.sup.14, COOR.sup.14, OCOR.sup.14, NR.sup.14R.sup.14, CONR.sup.14R.sup.14, NR.sup.14COR.sup.14, S(O).sub.2OR.sup.14 and S(O).sub.2O.sup.Z.sup.+, where aryl, the aryl moiety of aralkyl, aralkenyl and aralkynyl, heteroaryl, heterocyclyl, cycloalkyl, cycloalkenyl and cycloalkynyl may carry substituents selected from the group consisting of C.sub.1-C.sub.20-alkyl, C.sub.2-C.sub.20-alkenyl, C.sub.2-C.sub.20-alkynyl, C.sub.7-C.sub.20-aralkyl, C.sub.8-C.sub.20-aralkenyl, C.sub.8-C.sub.20-aralkynyl, C.sub.4-C.sub.20-cycloalkyl, C.sub.5-C.sub.20-cycloalkenyl, C.sub.6-C.sub.20-cycloalkynyl, halogen, SR.sup.14, OR.sup.14, COOR.sup.14, OCOR.sup.14, NR.sup.14R.sup.14, CONR.sup.14R.sup.14, NR.sup.14COR.sup.14, S(O).sub.2OR.sup.14 and S(O).sub.2O.sup.Z.sup.+, where R.sup.14 has one of the meanings given for R.sup.14.

3. The electrode layer according to claim 2, where D is a radical of the formula D.1, where R.sup.17 and R.sup.18 are independently of each other selected from the group consisting of C.sub.1-C.sub.8-alkyl, C.sub.2-C.sub.8-alkenyl, C.sub.6-C.sub.20-aryl, heteroaryl, C.sub.7-C.sub.20-aralkyl, C.sub.8-C.sub.20-aralkenyl, C.sub.8-C.sub.10-aralkynyl and C.sub.5-C.sub.12-cycloalkyl, where alkyl or alkenyl may be unsubstituted or may carry 1, 2 or 3 substituents selected from the group consisting of tetrahydrofuranyl, halogen, SR.sup.14, OR.sup.14, COOR.sup.14, OCOR.sup.14, NR.sup.14R.sup.14, CONR.sup.14R.sup.14 and NR.sup.14COR.sup.14, where aryl, heteroaryl, the aryl moiety of aralkyl, aralkenyl and aralkynyl and cycloalkyl are unsubstituted or may carry substituents selected from C .sub.1-C.sub.8-alkyl, C.sub.2-C.sub.8-alkenyl and C.sub.8-C.sub.20-aralkenyl; or R.sup.17 and R.sup.20 may form together with the nitrogen atom to which R.sup.17 is attached and the carbon atoms of the benzene ring to which R.sup.20 and NR.sup.17 are attached a 5-, 6- or 7-membered, saturated or unsaturated heterocycle which may have 1 further heteroatom selected from O, S and N as ring member and wherein the heterocycle may be unsubstituted or may carry one or more substituents R.sup.X4 selected from C.sub.1-C.sub.20-alkyl and phenyl, in addition two radicals R.sup.x4 bonded to adjacent carbon atoms may form together with the carbon atoms to which they are bonded a 4-, 5-, 6- or 7-membered saturated or unsaturated carbocyclic ring or an aromatic ring selected from benzene and 9H-fluorene where the carbocyclic and the aromatic ring are unsubstituted or carry one or more substituents selected from C.sub.1-C.sub.6-alkyl and fluoren-9-ylidenemethyl, and/or two radicals R.sup.x4 present on the same carbon atom may be C.sub.1-C.sub.20-alkylidene; R.sup.15 is selected from hydrogen, NR.sup.25R.sup.26, OR.sup.25, SR.sup.25, OCOR.sup.25 and NR.sup.25COR.sup.26; and R.sup.19, R.sup.20 and R.sup.21 are hydrogen, wherein R.sup.14 has one of the meanings given for R.sup.14.

4. The electrode layer according to claim 1, where D is a radical of the formula D.1, where R.sup.17 and R.sup.18 are independently of each other selected from the group consisting of C.sub.1-C.sub.8-alkyl, phenyl which is unsubstituted or carries 1 or 2 substituents selected from C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.4-alkoxy, 2-phenylvinyl, 2,2-diphenyl-vinyl and triphenylvinyl, 9H-fluoren-2-yl, which is unsubstituted or carries 1, 2 or 3 substituents selected from C.sub.1-C.sub.6-alkyl, pyrenyl, which is unsubstituted or carries 1 or 2 substituents selected from C.sub.1-C.sub.6-alkyl; or R.sup.17 and R.sup.18 together with the nitrogen atom to which they are attached are morpholinyl; or R.sup.17 and R.sup.20 form together with the nitrogen atom to which R.sup.17 is attached and the carbon atoms of the benzene ring to which R.sup.20 and NR.sup.17 are attached a 5- or 6-membered, nitrogen heterocycle which is unsubstituted or carries 2 radicals R.sup.x, where two radicals R.sup.X on two adjacent carbon atoms form together with the carbon atoms they are bonded to a 4-, 5-, 6-, or 7-membered saturated ring or a benzene ring, R.sup.15 is hydrogen, C.sub.1-C.sub.20-alkyl or OR.sup.25; and R.sup.19, R.sup.20 and R.sup.21 are hydrogen.

5. The electrode layer according to claim 4, where D is a radical of the formula D.1, where R.sup.15, R.sup.19, R.sup.20 and R.sup.21 are each hydrogen and R.sup.17 and R.sup.18 are independently of each other selected from the group consisting of C.sub.1-C.sub.6-alkyl, 9H-fluoren-2-yl and 9,9-di(C.sub.1-C.sub.8-alkyl)-9H-fluoren-2-yl or D is a radical of the formula D.1 selected from radicals of the formulae D.1-1 and D.1-2 ##STR00149## wherein * denotes the point of attachment to the remainder of the molecule and R.sup.18 is phenyl which is substituted by 2-phenylvinyl or 2,2-diphenylvinyl, 9H-fluoren-2-yl or 9,9-di(C.sub.1-C.sub.8-alkyl)-9H-fluoren-2-yl.

6. The electrode layer according to claim 1, where A is selected from the group of radicals consisting of the formulae A.1.1a, A.1.1b, A.2, A.3, A.4 and A.5 ##STR00150## where # denotes the bond to the remaining compound of formula I.

7. The electrode layer according to claim 1, where A is selected from the group of radicals consisting of the formulae A.1.1a, A.1.1b, A.2, A.3 and A.4 where R.sup.29 is selected from the group consisting of a radical G, C.sub.1-C.sub.20-alkyl which is uninterrupted or interrupted by O, S, CO, NR.sup.14 or combinations thereof, C.sub.6-C.sub.20-aryl, heteroaryl, C.sub.7-C.sub.20-aralkyl, C.sub.6-C.sub.20-aryl substituted by 1, 2 or 3 C.sub.1-C.sub.8-alkyl, and C.sub.7-C.sub.20-aralkyl wherein the aryl moiety of aralkyl is substituted by 1, 2 or 3 C.sub.1-C.sub.8-alkyl; R.sup.30 is selected from the group consisting of a radical G, hydrogen, C.sub.1-C.sub.20-alkyl wherein alkyl is uninterrupted or interrupted by O, S, CO, NR.sup.14 or combinations thereof, C.sub.6-C.sub.20-aryl, heteroaryl, and C.sub.6-C.sub.20-aryl wherein the aryl moiety of aralkyl is substituted by 1, 2 or 3 C.sub.1-C.sub.8-alkyl; R.sup.31 is selected from hydrogen and a radical of the formula D* ##STR00151## where #* denotes the point of attachment to the remainder of the molecule, m is 1, 2, 3, 4, 5 or 6; R.sup.32, R.sup.33, R.sup.34 and R.sup.35 are independently selected from the group consisting of hydrogen, C.sub.1-C.sub.20-alkyl wherein alkyl is uninterrupted or interrupted by O, S, NR.sup.14 or combinations thereof, C.sub.6-C.sub.20-aryl, heteroaryl, and C.sub.6-C.sub.20-aryl wherein the aryl moiety of aralkyl is substituted by 1, 2 or 3 C.sub.1-C.sub.8-alkyl; and G is selected from the group consisting of R.sup.28COOH, R.sup.28COO.sup.Z.sup.+; R.sup.28SO.sub.3H, R.sup.28SO.sub.3.sup.Z.sup.+; R.sup.28OP(O)(O.sup.Z.sup.+).sub.2, R.sup.28OP(O)(OH).sub.2 and R.sup.28OP(O)(OH)O.sup.Z.sup.+, where R.sup.28 is a direct bond, C.sub.1-C.sub.20-alkylene, C.sub.2-C.sub.4-alkenylene or C.sub.6-C.sub.10-arylene and Z.sup.+ is N(R.sup.14).sub.4.sup.+, or an alkali metal cation.

8. The electrode layer according to claim 7, wherein A is a radical of the formula A.1.1a, ##STR00152## where R.sup.29 is R.sup.28COOH or R.sup.28COO.sup.Z.sup.+, where R.sup.28 is a direct bond, C.sub.1-C.sub.4-alkylene, C.sub.2-C.sub.4-alkenylene or phenylene; and Z.sup.+ is N(R.sup.14).sub.4.sup.+, Li.sup.+, Na.sup.+ or K.sup.+; R.sup.14 is hydrogen or C.sub.1-C.sub.20-alkyl.

9. The electrode layer according to claim 7, where Y.sup. is a fluorinated organic anion selected from the group consisting of Y.1, Y.2, Y.3, Y.4, Y.5 and Y.6, where X.sup. is S(O).sub.2O.sup., OS(O).sub.2O.sup., or COO.sup.; Rf.sup.1 is fluorine, C.sub.1-C.sub.20-alkyl, C.sub.1-C.sub.20-haloalkyl, where the C.sub.1-C.sub.20-alky and C.sub.1-C.sub.20-haloalkyl are uninterrupted or interrupted by O, S, NR.sup.14, CO or combinations thereof and/or are unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, OR.sup.25, OCOR.sup.25, OCOOR.sup.25, OCONR.sup.25R.sup.26, COOR.sup.25 and CONR.sup.25R.sup.26, Rf.sup.2, Rf.sup.3, Rf.sup.4, Rf.sup.5 and Rf.sup.6 are independently selected from the group consisting of fluorine, hydrogen, OR.sup.25, OCOR.sup.25, OCOOR.sup.25, OCONR.sup.25R.sup.26, C.sub.1-C.sub.20-fluoroalkyl; X.sup.1, X.sup.2 and X.sup.3 are independently selected from S(O).sub.2 and CO; Rf.sup.7, Rf.sup.7*, Rf.sup.8, Rf.sup.8* and Rf.sup.9 are independently selected from the group consisting of C.sub.6-C.sub.20-fluoroaryl, C.sub.1-C.sub.20-fluoroalkyl and C.sub.1-C.sub.20-fluoroalkyl which is interrupted by O, S, NR.sup.14, CO or combinations thereof, wherein C.sub.1-C.sub.20-fluoroalkyl and interrupted C.sub.1-C.sub.20-fluoroalkyl are unsubstituted or substituted by one or more radicals selected from OR.sup.25, OCOR.sup.25, OCOOR.sup.25, OCONR.sup.25R.sup.26, COOR.sup.25 and CONR.sup.25R.sup.26, or Rf.sup.7 and Rf.sup.8 together are C.sub.3-C.sub.6-fluoroalkyl, Rf.sup.10, Rf.sup.11, Rf.sup.12 and Rf.sup.13 are independently selected from fluorine, C.sub.1-C.sub.20-fluoroalkyl and C.sub.6-C.sub.20-fluoroaryl, R.sup.f14 and R.sup.f15 are together C.sub.3-C.sub.5-perfluoroalkyl where the fluorine atoms of the last mentioned group may be replaced by C.sub.1-C.sub.10-fluoroalkyl.

10. The electrode layer according to claim 9, where Y.sup.31 is selected from the group consisting of a radical Y.1a, Y.1b, Y.2a, Y.3a, Y.4a, Y.5a and Y.6a ##STR00153## where Rf.sup.1 is fluorine, C.sub.1-C.sub.10-fluoroalkyl or C.sub.1-C.sub.10-fluoroalkyl which is substituted by OC(O)R.sup.25, where R.sup.25 is C.sub.1-C.sub.20-alkyl, phenyl which is unsubstituted or substituted by one or more C.sub.1-C.sub.20-alkoxy, where the alkyl moiety of alkoxy is interrupted by one or more oxygen atoms, or 6-, 7-, 8- or 9-membered saturated heterocyclyl with 1 or 2 heteroatoms or heteroatom groups selected from N, O, C(O), S, SO and SO.sub.2, as ring members, where heterocyclyl is unsubstituted or maycarry 1, 2, 3 , 4, 5 or 6 C.sub.1-C.sub.4-alkyl groups; Rf.sup.4 is OC(O)C.sub.1-C.sub.10-alkyl; Rf.sup.7 and Rf.sup.8 are independently of each other selected from C.sub.1-C.sub.6-fluroroalkyl or R.sup.f7 and R.sup.f8 taken together are C.sub.3-C.sub.6-fluoroalkyl, X.sup.1, X.sup.2 and X.sup.3 are each SO.sub.2, Rf.sup.7*, Rf.sup.8*, and R.sup.f9 are independently of each other selected from C.sub.1-C.sub.6-fluoroalkyl; Rf.sup.10, Rf.sup.11, Rf.sup.12 and Rf.sup.13 are each pentafluorophenyl; and Rf.sup.14a is C.sub.1-C.sub.6-fluoroalkyl.

11. The electrode layer according to claim 10, where A is a radical of the formula A.1a, where R.sup.29 is CH.sub.2COOH, and Y.sup. is selected from the group consisting of B(C.sub.6F.sub.5).sub.4.sup., Y.1a, Y.1b, Y.2a, Y.3a, Y.4a and Y.6a.

12. The electrode layer according to claim 1, where R.sup.1 and R.sup.2 are independently selected from the group consisting of hydrogen, C.sub.1-C.sub.20-alkyl which is uninterrupted or interrupted by O, S, CO, NR.sup.14 or combinations thereof, C.sub.6-C.sub.20-aryl, heteroaryl, and C.sub.6-C.sub.20-aryl which is substituted by 1, 2 or 3 C.sub.1-C.sub.8-alkyl; and R.sup.1 may also be a radical of the formula D.

13. The electrode layer according to claim 11, where R.sup.2 is hydrogen, C.sub.1-C.sub.20-alkyl or C.sub.6-C.sub.20-aryl; and R.sup.1 is hydrogen, C.sub.1-C.sub.20-alkyl, C.sub.6-C.sub.20-aryl or a radical of the formula D.

14. The electrode layer according to claim 1, wherein R.sup.1 and R.sup.2 are hydrogen.

15. The electrode layer according to claim 1, wherein n is 1 or 2.

16. The electrode layer according to claim 1, wherein n is 1; R.sup.1 and R.sup.2 are independently of each other selected from hydrogen or C.sub.1-C.sub.10-alkyl; D is a radical of the formula D.1, where R.sup.15 is hydrogen or C.sub.1-C.sub.20-alkoxy; R.sup.19, R.sup.20 and R.sup.21 are each hydrogen, R.sup.17 and R.sup.18 together with the nitrogen atom to which they are attached are morpholinyl, thiomorpholinyl, piperidinyl, piperazinyl, pyrrolidinyl, pyrrazolidinyl or imidazolidinyl, or R.sup.17 and R.sup.18 are independently of each other selected from the group consisting of C.sub.1-C.sub.6-alkyl, 9H-fluoren-2-yl, 9,9-di(C.sub.1-C.sub.8-alkyl)-9H-fluoren-2-yl, pyrenyl, pyrenyl which is substituted by C.sub.1-C.sub.6-alkyl.sub.1 and phenyl which is substituted by 2-phenylvinyl, 2,2-diphenylvinyl or triphenylvinyl or D is a radical of the formulae D.1-1 or D.1-2 ##STR00154## wherein * denotes the point of attachment to the remainder of the molecule and R.sup.18 is phenyl which is substituted by 2-phenylvinyl, 2,2-diphenylvinyl, 9H-fluoren-2-yl or 9,9-di(C.sub.1-C.sub.8-alkyl)-9H-fluoren-2-yl; A is a radical of the formula A.1.1a, ##STR00155## where R.sup.29 is R.sup.28COOH or R.sup.28COO.sup.Z.sup.+, where R.sup.28 is a direct bond, C.sub.1-C.sub.4-alkylene, C.sub.2-C.sub.4-alkenylene or phenylene; and Z.sup.+ is N(R.sup.14).sub.4.sup.+, Li.sup.+, Na.sup.+ or K.sup.+; where R.sup.14 is hydrogen or C.sub.1-C.sub.20-alkyl; and Y.sup. is selected from the group consisting of B(C.sub.6F.sub.5).sub.4.sup., [(C.sub.1-C.sub.4-perfluoroalkyl)SO.sub.2].sub.2N.sup., [(C.sub.1-C.sub.4-perfluoroalkyl)SO.sub.2].sub.3C.sup., C.sub.1-C.sub.8-perfluoroalkyl-SO.sub.3.sup. ##STR00156## where R.sup.25 is C.sub.1-C.sub.20-alkyl, phenyl which is unsubstituted or substituted by C.sub.1-C.sub.20-alkoxy, or 6- , 7-, 8- or 9-membered saturated heterocyclyl containing 1 or 2 heteroatoms or heteroatom groups selected from O, C(O), as ring members, where heterocyclyl is unsubstituted or may carry 1, 2, 3, 4, 5 or 6 C.sub.1-C.sub.4-alkyl groups, where C.sub.1-C.sub.20-alkoxy may be interrupted by one or more oxygen atoms, and Rf.sup.14a is C.sub.1-C.sub.3-perfluoroalkyl.

17. The electrode layer according to claim 1, wherein the oxide semiconductor fine particles comprise TiO.sub.2, SnO.sub.2, WO.sub.3, ZnO, Nb.sub.2O.sub.5, Fe.sub.2O.sub.3, ZrO.sub.2, MgO, WO.sub.3, ZnO, CdS, ZnS, PbS, Bi.sub.2S.sub.3, CdSe, CdTe or combinations thereof.

18. The electrode layer according to claim 1, wherein the porous film which comprises oxide semiconductor fine particles is sensitized with a dye of formula (I) and one or more further dyes.

19. The electrode layer according to claim 18, wherein the further dye is a metal complex dye and/or an organic dye selected from the group consisting of indoline, courmarin, cyanine, merocyanine, hemicyanine, methin, azo, quinone, quinonimine, diketo-pyrrolo-pyrrole, quinacridone, squaraine, triphenylmethane,perylene, indigo, xanthene, eosin, rhodamine and combinations thereof.

20. The electrode layer according to claim 1, wherein the dye is adsorbed together with an additive.

21. The electrode layer according to claim 20, wherein the additive is an adsorbent, a steroid, a crown ether, a cyclodextrine,a calixarene, a polyethyleneoxide, a hydroxamic acid, a hydroxamic acid derivative or combinations thereof.

22. A photoelectric conversion device comprising the electrode layer as defined in claim 1.

23. A dye sensitized solar cell comprising a photoelectric conversion device as defined in claim 22.

Description

EXAMPLE D-1

(1) D-1 is prepared according to the scheme below.

(2) ##STR00048## ##STR00049##

(3) Preparation of the Quinolinium Salt (A):

(4) A mixture of 4-methylquinoline (7.17 g, 50.07 mmol)), t-butyl bromoacetate (10.4 ml, 70.44 mmol)) and 150 ml of toluene were stirred overnight at 80 C. under N.sub.2. The precipitate was collected by filtration, washed by toluene and dried, giving beige solid (A) (13.6 g). The crude was used without further purification.

(5) Preparation of the Quinolinium Salt (C):

(6) A mixture of aldehyde (B) (1.0 g, 6.7 mmol), quinolinium salt (A) (1.8 g, 7.0 mmol) and 10 ml of acetic anhydride stirred at 80 C. under N.sub.2 for 2 hours. Acetic anhydride was removed by vacuum evaporation and the obtained solid was purified by column chromatography (silica gel, DCM-methanol (10->20%)), giving 1.4 g of (C).

(7) Preparation of the Quinolinium Salt (D):

(8) A mixture of quinolinium salt (C) (1.4 g) and 20 ml of dichloromethane/trifluoroacetic acid (4:3) was stirred at room temperature for 2 hours. Solvents were removed by vacuum evaporation and the obtained solid was purified by column chromatography (silica gel, DCM-methanol (5->20%)), giving 1.1 g of (D).

(9) Preparation of D-1

(10) A mixture of quinolinium salt (D) (150 mg, 0.36 mmol), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) (206 mg, 0.72 mmol) and dichloromethane (5 ml)/H.sub.2O (5 ml) was stirred at room temperature for 17 hours. Dichloromethane was removed by vacuum evaporation, yielding a water suspension of dye D-1. The dye was collected by filtration and washed by water and was dried in vacuo at room temperature overnight, giving 150 mg of D-1.

(11) The procedures described in the synthesis example above were used to prepare further compounds D-2 to D-21 by appropriate modification of the starting compounds. The compounds thus obtained are listed in table I below, together with physicochemical data.

EXAMPLE D-2 to D-4

(12) Dyes D-2, D-3 and D-4 were prepared in analogy to the above-mentioned procedures except using corresponding salt of counter anion in place of LiTFSI.

EXAMPLE D-5

(13) ##STR00050##

(14) Dyes D-5 was prepared in analogy to the above-mentioned procedures except using corresponding aldehyde (E) in place of (B).

EXAMPLE D-6 to D-9

(15) Dyes D-6 to D-9 were prepared in analogy to the procedure of D-5 except using corresponding salt of counter anion in place of LiTFSI.

EXAMPLE D-10

(16) Dyes D-10 was prepared in analogy to the procedure of D-1 except using corresponding salt of counter anion in place of LiTFSI.

EXAMPLE D-11 TO D-13

(17) Dyes D-11 to D-13 were prepared in analogy to the procedure of D-5 except using corresponding salt of counter anion in place of LiTFSI.

EXAMPLE D-14 TO D-16

(18) ##STR00051##

(19) Dyes D-14 to D-16 were prepared in analogy to the above-mentioned procedures except using corresponding aldehyde (F), (G) and (H), respectively.

(20) Dyes D-17 to D-29 are prepared in analogy to the above-mentioned procedures.

(21) TABLE-US-00001 TABLE I Chemical Structure No. Donor Spacer/Acceptor D-1 D-2 D-3 D-4 D-5 0 D-6 D-7 D-8 D-9 D-10 0 D-11 D-12 D-13 D-14 D-15 0 D-16 D-17 D-18 D-19 D-20 0 D-21 D-22 D-23 D-24 D-25 00 01 D-26 02 03 D-27 04 05 D-28 06 07 D-29 08 09 Absorption spectrum Chemical Structure .sub.max Anion (nm) D-1 0 542 37500 D-2 541 41500 D-3 541 46300 D-4 542 45500 D-5 584 59000 D-6 585 63500 D-7 584 57400 D-8 583 58900 D-9 PF.sub.6.sup. 585 51500 D-10 541 40200 D-11 584 54400 D-12 0 584 69600 D-13 584 64600 D-14 553 30200 D-15 587 64100 D-16 585 60100 D-17 542 34200 D-18 584 50200 D-19 585 57200 D-20 541 45800 D-21 542 47400 D-22 0 543 32300 D-23 585 63100 D-24 583 55800 D-25 584 67900 D-26 583 56900 D-27 581 37800 D-28 583 40900 D-29 579 52600

(22) Performance Results

EXAMPLE A-1

Preparation of DSC Device

(23) FTO (tin oxide doped with fluorine) glass substrates (<12 ohms/sq, A11DU80, supplied by AGC Fabritech Co., Ltd.) were used as the base material, which were successively treated with glass cleaner, Semico Clean (Furuuchi Chemical Corporation), fully deionized water and acetone, in each case for 5 min in an ultrasonic bath, then baked for 10 minutes in isopropanol and dried in a nitrogen flow.

(24) A spray pyrolysis method was used to produce the solid TiO2 buffer layer. Titanium oxide paste (PST-18NR, supplied by Catalysts & Chemicals Ind. Co., Ltd.) was applied onto the FTO glass substrate by screen printing method. After being dried for 5 minutes at 120 C., a working electrode layer having a thickness of 1.6 m was obtained by applying heat treatment in air at 450 C. for 30 minutes and 500 C. for 30 minutes. Obtained working electrode is then treated with TiCl.sub.4, as described by M. Grtzel et al., for example, in Grtzel M. et al., Adv. Mater. 2006, 18, 1202. After sintering the sample was cooled to 60 to 80 C. The sample was then treated with additive (E-1) shown below (EP 10167649.2).

(25) ##STR00138##

(26) 5 mM of (E-1) in ethanol was prepared and the intermediate was immersed for 17 hours, washed in a bath of pure ethanol, briefly dried in a nitrogen stream and subsequently immersed in a 0.5 mM solution of dye (D-1) in a mixture solvent of acetonitrile+t-butyl alcohol (1:1) for 2 hours so as to adsorb the dye. After removal from the solution, the specimen was subsequently washed in acetonitrile and dried in a nitrogen flow.

(27) A p-type semiconductor solution was spin-coated on next. To this end a 0.165M 2,2,7,7-tetrakis(N,N-di-p-methoxyphenyl-amine)-9,9-spirobifluorene (spiro-MeOTAD) and 20 mM LiN(SO.sub.2CF.sub.3).sub.2 (Wako Pure Chemical Industries, Ltd.) solution in chlorobenzene was employed. 20 ll/cm.sup.2 of this solution was applied onto the specimen and allowed to act for 60 s. The supernatant solution was then spun off for 30 s at 2000 revolutions per minute. The substrate was stored overnight under ambient conditions. Thus, the HTM was oxidized and for this reason the conductivity increased.

(28) As the metal back electrode, Ag was evaporated by thermal metal evaporation in a vacuum at a rate of 0.5 nm/s in a pressure of 110.sup.5 mbar, so that an approximately 100 nm thick Ag layer was obtained.

(29) In order to determine the photo-electric power conversion efficiency of the above photoelectric conversion device, the respective current/voltage characteristic such as short-circuit current density J.sub.sc, open-circuit voltage V.sub.oc and fill factor FF. was obtained with a Source Meter Model 2400 (Keithley Instruments Inc.) under the illumination of an artificial sunlight (AM 1.5, 100 mW/cm.sup.2 intensity) generated by a solar simulator (Peccell Technologies, Inc).

EXAMPLES A-2 to A-4

(30) DSC device was prepared and evaluated in the same manner as described in the example A-1 except that the compound (D-1) was replaced with a compound (D-2) to (D-4).

COMPARATIVE EXAMPLE A-5 to A-6

(31) DSC device was prepared and evaluated in the same manner as described in the example A-1 except that the compound (D-1) was replaced with a compound (R-1) to (R-2) shown below. Compounds R-1 and R-2 are not according to the invention and serve as comparison compounds. Compounds R-1 and R-2 only differ in the counter anion from compounds according to the invention.

(32) Table 1 shows the results.

(33) TABLE-US-00002 TABLE 1 Solid DSC performance (R-1) 0 (R-2) Example Compound Jsc [mA/cm.sup.2] Voc [mV] FF. [%] [%] A-1 D-1 7.1 741 65 3.4 A-2 D-2 8.6 655 55 3.1 A-3 D-3 7.2 691 57 2.9 A-4 D-4 8.4 683 49 2.8 A-5 R-1** 7.6 587 60 2.7 A-6 R-2 6.2 586 51 1.8 **Included in the claim of CN1534021, but not example

(34) As can be seen from table 1, compounds I with a fluorinated counter anion (A-1 to A-4) show higher Jsc and Voc, giving higher energy conversion efficiency than comparative compounds R-1 and R-2 with Br and C.sub.8H.sub.17SO.sub.3.sup. as counter anion for the same chromophore.

EXAMPLES A-7 to A-18

(35) DSC device is prepared and evaluated in the same manner as described in the example A-1 except that the compound (D-1) is replaced with a compound (D-5) to (D-9) and (D-23) to (D-29).

COMPARATIVE EXAMPLE A-19

(36) DSC device is prepared and evaluated in the same manner as described in the example A-1 except that the compound (D-1) is replaced with a compound (R-3) shown below. Compound R-3 only differs in the counter anion from compounds according to the invention. Table 2 shows the results.

(37) TABLE-US-00003 TABLE 2 Solid DSC performance (R-3) Example Compound Jsc [mA/cm.sup.2] Voc [mV] FF. [%] [%] A-7 D-5 10.5 721 59 4.5 A-8 D-6 11.0 759 58 4.8 A-9 D-7 11.0 750 48 4.0 A-10 D-8 11.0 712 61 4.8 A-11 D-9 9.8 710 66 4.6 A-12 D-23 11.3 724 58 4.7 A-13 D-24 12.5 685 49 4.2 A-14 D-25 11.7 713 58 4.8 A-15 D-26 12.4 686 55 4.7 A-16 D-27 11.4 736 63 5.3 A-17 D-28 12.2 746 55 5.0 A-18 D-29 13.3 718 52 5.0 A-19 R-3 11.9 663 47 3.7

(38) As can be seen from table 2, compounds I with fluorinated counter anions (A-7 to A-18) show higher Voc, giving higher energy conversion efficiency than the comparison compound R-3 with bromine as counter anion (A-19) for the same chromophore.