Quinolinium dyes with fluorinated counter anion for dye sensitized solar cells

An electrode layer comprising a porous film which comprises oxide semiconductor fine particles sensitized with a dye of formula (I),

• where
• n is 1, 2, 3, 4, 5 or 6;
• R1 and R2 are independently of each other selected from the group consisting of hydrogen, C1-C20-alkyl wherein alkyl is uninterrupted or interrupted by O, S, CO, NR14 or combinations thereof, C6-C20-aryl, heteroaryl and C6-C20-aryl which has 1, 2 or 3 substituents selected from C1-C8-alkyl, and
• R1 can additionally be a radical of formula D;
• D is independently selected from a radical of formulae D.1 and D.2
• where
• * denotes the bond to the remaining compound of formula I,
• R17 and R18 are independently of each other selected from unsubstituted or substituted C1-C20-alkyl, unsubstituted or substituted C2-C20-alkenyl, unsubstituted or substituted C2-C20-alkynyl, unsubstituted or substituted C7-C20-aralkyl, unsubstituted or substituted C8-C20-aralkenyl, unsubstituted or substituted C8-C20-aralkynyl, unsubstituted or substituted C6-C20-aryl, unsubstituted or substituted heteroaryl, unsubstituted or substituted heterocyclyl, unsubstituted or substituted C4-C20-cycloalkyl, unsubstituted or substituted C5-C20-cycloalkenyl and unsubstituted or substituted C6-C20-cycloalkynyl, wherein alkyl, alkenyl, alkynyl or the aliphatic moieties in aralkyl, aralkenyl or aralkynyl are uninterrupted or interrupted by O, S, CO, NR14 or combinations thereof, where R14 is hydrogen, C1-C20-alkyl or C6-C10-aryl;
• or
• R17 and R18 form together with the nitrogen atom to which they are attached an unsubstituted or substituted 5-, 6- or 7-membered ring;
• or
• R17 and R20 form together with the nitrogen atom to which R17 is attached and the carbon atoms of the benzene ring to which R20 and N—R17 are attached an unsubstituted or substituted 5-, 6- or 7-membered ring;
• or
• R17 and R22 form together with the nitrogen atom to which R17 is attached and the carbon atoms of the benzene ring to which R22 and N—R17 are attached an unsubstituted or substituted 5-, 6- or 7-membered ring;
• and/or
• R18 and R19 form with the nitrogen atom to which R18 is attached and the carbon atoms of the benzene ring to which R19 and N—R18 are attached an unsubstituted or substituted 5-, 6- or 7-membered ring;
• R15, R16, R19, R20, R21, R22, R23 and R24 are independently of each other selected from the group consisting of hydrogen, NR25R26, OR25, SR25, NR25—NR26R27, NR25—OR26, O—CO—R25, O—CO—OR25, O—CO—NR25R26, NR25—CO—R26, NR25—CO—OR26, NR25—CO—NR26R27, CO—R25, CO—OR25, CO—NR25R26, S—CO—R25, CO—SR25, CO—NR25—NR26R27, CO—NR25—OR26, CO—O—CO—R25, CO—O—CO—OR25, CO—O—CO—NR25R26, CO—NR25—CO—R26, CO—NR25—CO—OR26, unsubstituted or substituted C1-C20-alkyl, unsubstituted or substituted C2-C20-alkenyl, unsubstituted or substituted C2-C20-alkynyl, unsubstituted or substituted C7-C20-aralkyl, unsubstituted or substituted C8-C20-aralkenyl, unsubstituted or substituted C8-C20-aralkynyl, unsubstituted or substituted C6-C20-aryl, unsubstituted or substituted heteroaryl, unsubstituted or substituted heterocyclyl, unsubstituted or substituted C4-C20-cycloalkyl, unsubstituted or substituted C5-C20-cycloalkenyl and unsubstituted or substituted C6-C20-cycloalkynyl,
• wherein alkyl, alkenyl, alkynyl or the aliphatic moieties in aralkyl, aralkenyl or aralkynyl are uninterrupted or interrupted by O, S, CO, NR14 or combinations thereof;
• R25, R26 and R27 are independently of each other selected from hydrogen, unsubstituted or substituted C1-C20-alkyl, unsubstituted or substituted C2-C20-alkenyl, unsubstituted or substituted C2-C20-alkynyl, unsubstituted or substituted C7-C20-aralkyl, unsubstituted or substituted C8-C20-aralkenyl, unsubstituted or substituted C8-C20-aralkynyl, unsubstituted or substituted C6-C20-aryl, unsubstituted or substituted heteroaryl, unsubstituted or substituted heterocyclyl, unsubstituted or substituted C4-C20-cycloalkyl, unsubstituted or substituted C5-C20-cycloalkenyl and unsubstituted or substituted C6-C20-cycloalkynyl,
• wherein alkyl, alkenyl, alkynyl or the aliphatic moieties in aralkyl, aralkenyl or aralkynyl are uninterrupted or interrupted by O, S, CO, NR14 or combinations thereof;
• A is a radical of formulae A.1, A.2, A.3, A.4 or A.5
• where
• # denotes the bond to the remaining compound of formula I
• R29, R30, R31, R32, R33, R34 and R35 are independently of each other selected from the group consisting of a radical G, hydrogen, halogen, OR36, unsubstituted or substituted unsubstituted or substituted C1-C20-alkyl, unsubstituted or substituted C2-C20-alkenyl, unsubstituted or substituted C2-C20-alkynyl, unsubstituted or substituted C7-C20-aralkyl, unsubstituted or substituted C8-C20-aralkenyl, unsubstituted or substituted C8-C20-aralkynyl, unsubstituted or substituted C6-C20-aryl, unsubstituted or substituted heteroaryl, unsubstituted or substituted heterocyclyl, unsubstituted or substituted C5-C20-cycloalkyl, unsubstituted or substituted C5-C20-cycloalkenyl and unsubstituted or substituted C6-C20-cycloalkynyl,
• wherein alkyl, alkenyl, alkynyl or the aliphatic moieties in aralkyl, aralkenyl or aralkynyl are uninterrupted or interrupted by O, S, CO, NR14 or combinations thereof;
• with the proviso that at least one of the radicals R29, R30, R31, R32, R33, R34 and R35 is a radical G,
• where
• R36 is unsubstituted or substituted C1-C20-alkyl, unsubstituted or substituted C6-C20-aryl, unsubstituted or substituted heteroaryl, wherein alkyl is uninterrupted or interrupted by O, S, CO, NR14 or combinations thereof;
• G is selected from the group consisting of —R28—COOH, —R28—COO−Z+, —R28—CO(C═O)OH, —R28—CO(C═O)O−Z+, —R28—S(═O)2OH, —R28—S(═O)2O−Z+, —R2—O—S(═O)2OH, —R28—O—S(═O)2O−Z+, —R28—P(═O)(OH)2, —R28—P(═O)(O−Z+)2, —R28—P(═O)(OH)(O−Z+), —R28—O—P(═O)(OH)2, —R28—O—P(═O)(O−Z+)2, —R28—O—P(═O)(OH)(O−Z+), —R28—CO—NH—OH, —R28—S(═O)2NH—OH, —R28—NR14—S(═O)2OH and —R28—NR14—S(═O)2O−Z+;
• where
• R28 is a direct bond, C1-C20-alkylene, C2-C4-alkenylene or C6-C10-arylene;
• Z+ is an organic or inorganic cation equivalent;
• Y− is a fluorinated organic anion selected from Y.1, Y.2, Y.3, Y.4, Y.5 and Y.6;
• wherein
• X− is S(═O)2O−, O—S(═O)2O−, COO−,
• Rf1 is selected from the group consisting of halogen, unsubstituted or substituted C1-C20-alkyl, unsubstituted or substituted haloalkyl, unsubstituted or substituted C2-C20-alkenyl, unsubstituted or substituted haloalkenyl, unsubstituted or substituted C2-C20-alkynyl, unsubstituted or substituted haloalkynyl, unsubstituted or substituted C7-C20-aralkyl, unsubstituted or substituted C8-C20-aralkenyl, unsubstituted or substituted C8-C20-aralkynyl, unsubstituted or substituted C6-C20-aryl, unsubstituted or substituted heteroaryl, unsubstituted or substituted heterocyclyl, unsubstituted or substituted C4-C20-cycloalkyl, unsubstituted or substituted C5-C20-cycloalkenyl and unsubstituted or substituted C6-C20-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, NR14 or combinations thereof,
• Rf2, Rf3, Rf4, Rf5 and Rf6 are independently selected from the group consisting of halogen, hydrogen, NR25R26, OR25, SR25, NR25—NR26R27, NR25—OR26, O—CO—R25, O—CO—OR25, O—CO—NR25R26, NR25—CO—R26, NR25—CO—OR26, NR25—CO—NR26R27, CO—R25, CO—OR25, CO—NR25R26, S—CO—R25, CO—SR25, CO—NR25—NR26R27, CO—NR25—OR26, CO—O—CO—R25, CO—O—CO—OR25, CO—O—CO—NR25R26, CO—NR25—CO—R26, CO—NR25—CO—OR26, unsubstituted or substituted C1-C20-alkyl, unsubstituted or substituted C2-C20-alkenyl, unsubstituted or substituted C2-C20-alkynyl, unsubstituted or substituted C6-C20 aryl, unsubstituted or substituted heteroaryl, unsubstituted or substituted heterocyclyl, unsubstituted or substituted C7-C20-aralkyl, unsubstituted or substituted C8-C20-aralkenyl, unsubstituted or substituted C8-C20-aralkynyl, unsubstituted or substituted C4-C20-cycloalkyl, unsubstituted or substituted C5-C20-cycloalkenyl and unsubstituted or substituted C6-C20-cycloalkynyl,
• wherein alkyl, alkenyl, alkynyl or the aliphatic moieties in aralkyl, aralkenyl or aralkynyl are uninterrupted or interrupted by O, S, CO, NR14 or combinations thereof;
• with the proviso that at least one of the radicals Rf2, Rf3, Rf4, Rf5 and Rf6 is fluorine or C1-C20-fluoroalkyl, wherein fluoroalkyl is uninterrupted or interrupted by O, S, NR14, CO, or combinations thereof;
• X1, X2 and X3 are independently of each other selected from S(═O)2 and CO;
• Rf7, Rf7*, Rf8, Rr8* and Rf9 are independently of each other selected from the group consisting of unsubstituted or substituted C1-C20-fluoroalkyl, C6-C20-fluoroaryl, wherein fluoroalkyl is uninterrupted or interrupted by O, S, NR14, CO, or combinations thereof;
• or
• Rf7 and Rf8 together are C3-C6-fluoroalkyl;
• Rf10, Rf11, Rf12 and Rf13 are independently of each other selected from fluorine, C1-C20-fluoroalkyl and C6-C20-fluoroaryl;
• Rf14 and Rf15 together are C3-C7-fluoroalkyl which is unsubstituted or substituted by C1-C6-fluoroalkyl;
• Rg is unsubstituted or substituted C1-C20-alkyl, unsubstituted or substituted C1-C20-alkoxy, unsubstituted or substituted C6-C20-aryl or unsubstituted or substituted C6-C20aryl-O—, wherein alkyl and the alkyl moiety in alkoxy is uninterrupted or interrupted by O, S, NR14, CO, or combinations thereof;
• wherein Y− is not BF4−,
• with the proviso that if R17 and R18 are both unsubstituted or substituted fluorene, Y− is not bistrifluoromethylsulfonimide, C(SO2CF3)3−, and
• with the proviso that if A is a radical of the formula A.1.1c
• Y− is not (CnF2n+1SO2)2N−, where n is an integer from 1 to 18.