Use of Rylene Derivatives as Photosensitizers in Solar Cells

A rylene derivative of the general formula Ia

• in which the dicarboxylic anhydride radical may also represent two carboxyl radicals —COOM and the variables are each defined as follows:
• Y one of the two radicals is a radical of the formula (y 1)
• -L-NR1R2 (y1)
• or a radical of the formula (y2)
• -L-Z-R3 (y2)
• and the other radical in each case is hydrogen;
• are joined together with formation of a six-membered ring to give a radical of the formula (y3)
• R are identical or different radicals:
• aryloxy, arylthio, hetaryloxy or hetarylthio, to each of which may be fused further saturated or unsaturated 5- to 7-membered rings whose carbon skeleton may be interrupted by one or more —O—, —S—, —NR4—, —N═CR4—, —CO—, —SO— and/or —SO2— moieties, where the entire ring system may be mono- or polysubstituted by the (i), (ii), (iii), (iv) and/or (v) radicals:
• (i) C1-C30-alkyl whose carbon chain may be interrupted by one or more —O—, —S—, —NR4—, —N═CR4—, —C≡C—, —CR4═CR4—, —CO—, —SO— and/or —SO2— moieties and which may be mono- or polysubstituted by:
• C1-C12-alkoxy, C1-C6-alkylthio, —C≡CR4, —CR4═CR42, hydroxyl, mercapto, halogen, cyano, nitro, —NR9R10, —NR5COR6, —CONR5R6, —SO2NR5R6, —COOR7, —SO3R7, —PR72, —POR7R7, (het)aryl and/or saturated or unsaturated C4-C7-cycloalkyl whose carbon skeleton may be interrupted by one or more —O—, —S—, —NR4—, —N═CR4—, —CR4═CR4—, —CO—, —SO— and/or —SO2— moieties, where the (het)aryl and cycloalkyl radicals may each be mono- or polysubstituted by C1-C18-alkyl and/or the above radicals specified as substituents for alkyl;
• (ii) C3-C8-cycloalkyl whose carbon skeleton may be interrupted by one or more —O—, —S—, —NR4—, —N═CR4—, —CR4═CR4—, —CO—, —SO— and/or —SO2— moieties and to which may be fused further saturated or unsaturated 5- to 7-membered rings whose carbon skeleton may be interrupted by one or more —O—, —S—, —NR4—, —N═CR4—, —CR4═CR4—, —CO—, —SO— and/or —SO2— moieties, where the entire ring system may be mono- or polysubstituted by:
• C1-C18-alkyl, C1-C12-alkoxy, C1-C6-alkylthio, —C≡CR4, —CR4═CR42, hydroxyl, mercapto, halogen, cyano, nitro, —NR9R10, —NR5COR6, —CONR5R6, —SO2NR5R6, —COOR7, —SO3R7, —PR72 and/or —POR7R7;
• (iii) aryl or hetaryl to which may be fused further saturated or unsaturated 5- to 7-membered rings whose carbon skeleton may be interrupted by one or more —O—, —S—, —NR4—, —N═CR4—, —CR4═CR4—, —CO—, —SO— and/or —SO2— moieties, where the entire ring system may be mono- or polysubstituted by:
• C1-C18-alkyl, C1-C12-alkoxy, C1-C6-alkylthio, —C≡CR4, —CR4═CR42, hydroxyl, mercapto, halogen, cyano, nitro, —NR7R8, —NR5COR6, —CONR5R6, —SO2NR5R6, —COOR7, —SO3R7, —PR72, —POR7R7, (het)aryl, (het)aryloxy and/or (het)arylthio, where the (het)aryl radicals may each be mono- or polysubstituted by C1-C18-alkyl, C1-C12-alkoxy, C1-C6-alkylthio, hydroxyl, mercapto, halogen, cyano, nitro, —NR7R8, —NR5COR6, —CONR5R6, —SO2NR5R6, —COOR7, —SO3R7, —PR72 and/or —POR7R7;
• (iv) a —U-aryl radical which may be mono- or polysubstituted by the above radicals specified as substituents for the aryl radicals (iii), where U is a —O—, —S—, —NR3—, —CO—, —SO— or —SO2— moiety;
• (v) C1-C2-alkoxy, C1-C6-alkylthio, —C≡CR4, —CR4═CR42, hydroxyl, mercapto, halogen, cyano, nitro, —NR7R8, —NR5COR6, —CONR5R6, —SO2NR5R6, —COOR7, —SO3R7, —PR72 and/or —POR7R7;
• P is an amino radical —NR1R2;
• M is hydrogen, monovalent or divalent metal cation, especially alkaline earth metal or alkali metal cation, ammonium salts of cyclic amines, guanidinium salts or [NR5]4+;
• L is a chemical bond or an arylene or hetarylene radical, bonded to the rylene skeleton directly or via ethenylene or ethynylene, of the formulae
• —Ar— —Ar-E-Ar—
• in which the (het)arylene radicals Ar may be the same or different, may comprise heteroatoms as ring atoms and/or may have fused saturated or unsaturated 5- to 7-membered rings which may likewise comprise heteroatoms, where the entire ring system may be mono- or polysubstituted by phenyl, C1-C12-alkyl, C1-C12-alkoxy, C1-C12-alkylthio and/or —NR5R6;
• E is a chemical bond or an —O—, —S—, —NR4—, —C≡C—, —CR4═CR4— or C1-C6-alkylene moiety;
• R1, R2 are each independently one of the alkyl radicals (i), cycloalkyl radicals (ii) or (het)aryl radicals (iii) specified as substituents for the R radicals;
• joined together to form a saturated or unsaturated, 5- to 7-membered ring which comprises the nitrogen atom and whose carbon chain may be interrupted by one or more —O—, —S— and/or —NR4— moieties, to which may be fused one or two unsaturated or saturated 4- to 8-membered rings whose carbon chain may likewise be interrupted by these moieties and/or —N═, where the entire ring system may be mono- or polysubstituted by:
• C1-C24-alkyl which may be substituted by C1-C18-alkoxy, C1-C18-alkylthio and/or —NR5R6, (het)aryl which may be mono- or polysubstituted by C1-C18-alkyl and/or the aforementioned radicals as substituents for alkyl, C1-C18-alkoxy, C1-C18-alkylthio and/or —NR5R6;
• Z is —O— or —S—;
• R3 is one of the alkyl radicals (i) or (het)aryl radicals (iii) specified as substituents for the R radicals;
• R′ is C1-C30-alkyl whose carbon chain may be interrupted by one or more —O—, —S— and/or —NR4— moieties and which may be mono- or polysubstituted by:
• C1-C12-alkoxy, C1-C6-alkylthio, —NR9R10, (het)aryl and/or C4-C7-cycloalkyl whose carbon skeleton may be interrupted by one or more —O—, —S— and/or —NR4-moieties, where the cycloalkyl and (het)aryl radicals may be mono- or polysubstituted by C1-C18-alkyl and/or the above radicals specified as substituents for alkyl;
• aryl or hetaryl, to each of which may be fused further saturated or unsaturated 5- to 7-membered rings whose carbon skeleton may be interrupted by one or more —O—, —S— and/or —NR4— moieties, where the entire ring system is mono- or polysubstituted by —NR9R10;
• R4 is hydrogen or C1-C18-alkyl, where the R4 radicals may be the same or different when they occur more than once;
• R5, R6 are each independently:
• hydrogen;
• C1-C18-alkyl whose carbon chain may be interrupted by one or more —O—, —S—, —CO—, —SO— and/or —SO2— moieties and which may be mono- or polysubstituted by C1-C12-alkoxy, C1-C6-alkylthio, hydroxyl, mercapto, halogen, cyano, nitro and/or —COOR8;
• aryl or hetaryl to each of which may be fused further saturated or unsaturated 5- to 7-membered rings whose carbon skeleton may be interrupted by one or more —O—, —S—, —CO— and/or —SO2— moieties, where the entire ring system may be mono- or polysubstituted by C1-C12-alkyl and/or the above radicals specified as substituents for alkyl;
• where the R5 radicals may be the same or different when they occur more than once;
• R7 is C1-C18-alkyl whose carbon chain may be interrupted by one or more —O—, —S—, —CO—, —SO— and/or —SO2— moieties and which may be mono- or polysubstituted by C1-C12-alkoxy, C1-C6-alkylthio, hydroxyl, mercapto, halogen, cyano, nitro and/or —COOR8;
• aryl or hetaryl to each of which may be fused further saturated or unsaturated 5- to 7-membered rings whose carbon skeleton may be interrupted by one or more —O—, —S—, —CO— and/or —SO2— moieties, where the entire ring system may be mono- or polysubstituted by C1-C12-alkyl and/or the above radicals specified as substituents for alkyl,
• where the R7 radicals may be the same or different when they occur more than once;
• R8 is C1-C18-alkyl;
• R9, R10 are each C1-C30-alkyl whose carbon chain may be interrupted by one or more —O—, —S—, —NR4—, —N═CR4—, —C≡C—, —CR4═CR4—, —CO—, —SO— and/or —SO2-moieties and which may be mono- or polysubstituted by:
• C1-C12-alkoxy, C1-C6-alkylthio, —C≡CR4, —CR4═CR42, hydroxyl, —NR5R6, —NR5COR6, (het)aryl and/or saturated or unsaturated C4-C7-cycloalkyl whose carbon skeleton may be interrupted by one or more —O—, —S—, —NR4—, —N═CR4— and/or —CR4═CR4 moieties, where the (het)aryl and cycloalkyl radicals may each be mono- or polysubstituted by C1-C18-alkyl and/or the above radicals specified as substituents for alkyl;
• aryl or hetaryl to which may be fused further saturated or unsaturated 5- to 7-membered rings whose carbon skeleton may be interrupted by one or more —O—, —S—, —NR4—, —N═CR4—, —CR4═CR4—, —CO—, —SO— and/or —SO2— moieties, where the entire ring system may be mono- or polysubstituted by:
• C1-C18-alkyl, C1-C12-alkoxy, C1-C6-alkylthio, —C≡CR4, —CR4═CR42, hydroxyl, —NR5R6, —NR5COR6, (het)aryl, (het)aryloxy and/or (het)arylthio, where the (het)aryl radicals may in each case be mono- or polysubstituted by C1-C18-alkyl, C1-C12-alkoxy, hydroxyl, —NR5R6 and/or —NR5COR6
• joined to the nitrogen atom to form a saturated or unsaturated, 5- to 7-membered ring whose carbon chain may be interrupted by one or more —O—, —S— and/or —NR4— moieties, to which may be fused one or two unsaturated or saturated 4- to 8-membered rings whose carbon chain may likewise be interrupted by these moieties and/or —N═, where the entire ring system may be mono- or polysubstituted by:
• C1-C24-alkyl which may be substituted by C1-C18-alkoxy, C1-C18-alkylthio and/or —NR5R6, (het)aryl which may be mono- or polysubstituted by C1-C18-alkyl and/or the above radicals specified as substituents for alkyl, C1-C18-alkoxy, C1-C18-alkylthio and/or —NR5R6;
• m is 0, 1 or 2;
• n is 0, 2 or 4 when m=0;
• is 0, 2 or 4 when m=1;
• is 0, 4 or 6 when m=2;
• p is 0, 2 or 4 when m=0, where n+p=0, 2 or 4, where, in the case that n+p=0 and one of the two Y radicals is a radical of the formula (y1) and the other radical is hydrogen, at least one of the two R1 or R2 radicals is one of the (het)aryl radicals (iii) specified as substituents for the R radicals when L is a chemical bond;
• is 0, 2 or 4 when m=1, where n+p=0, 2 or 4;
• is 0, 4 or 6 when m=2, where n+p=0, 4 or 6.

A rylene derivative of the general formula Ib

• in which the variables are each defined as follows:
• X are joined to one another with formation of a six-membered ring to give a radical of the formula (x2) or (x3)
• Y one of the two radicals is a radical of the formula (y1)
• -L-NR1R2 (y1)
• or a radical of the formula (y2)
• -L-Z-R3 (y2)
• or one radical is R and the other radical in each case is hydrogen;
• are joined together with formation of a six-membered ring to give a radical of the formula (y3) or (y4)
• or both are hydrogen;
• R are identical or different radicals:
• aryloxy, arylthio, hetaryloxy or hetarylthio, to each of which may be fused further saturated or unsaturated 5- to 7-membered rings whose carbon skeleton may be interrupted by one or more —O—, —S—, —NR4—, —N═CR4—, —CO—, —SO— and/or —SO2— moieties, where the entire ring system may be mono- or polysubstituted by the (i), (ii), (iii), (iv) and/or (v) radicals:
• (i) C1-C30-alkyl whose carbon chain may be interrupted by one or more —O—, —S—, —NR4—, —N═CR4—, —C≡C—, —CR4═CR4—, —CO—, —SO— and/or —SO2— moieties and which may be mono- or polysubstituted by:
• C1-C12-alkoxy, C1-C6-alkylthio, —C≡CR4, —CR4═CR42, hydroxyl, mercapto, halogen, cyano, nitro, —NR9R10, —NR5COR6, —CONR5R6, —SO2NR5R6, —COOR7, —SO3R7, —PR72, —POR7R7, (het)aryl and/or saturated or unsaturated C4-C7-cycloalkyl whose carbon skeleton may be interrupted by one or more —O—, —S—, —NR4—, —N═CR4—, —CR4═CR4—, —CO—, —SO— and/or —SO2— moieties, where the (het)aryl and cycloalkyl radicals may each be mono- or polysubstituted by C1-C18-alkyl and/or the above radicals specified as substituents for alkyl;
• (ii) C3-C8-cycloalkyl whose carbon skeleton may be interrupted by one or more —O—, —S—, —NR4—, —N═CR4—, —CR4═CR4—, —CO—, —SO— and/or —SO2— moieties and to which may be fused further saturated or unsaturated 5- to 7-membered rings whose carbon skeleton may be interrupted by one or more —O—, —S—, —NR4—, —N═CR4—, —CR4═CR4—, —CO—, —SO— and/or —SO2— moieties, where the entire ring system may be mono- or polysubstituted by:
• C1-C18-alkyl, C1-C12-alkoxy, C1-C6-alkylthio, —C≡CR4, —CR4═CR42, hydroxyl, mercapto, halogen, cyano, nitro, —NR9R10, —NR5COR6, —CONR5R6, —SO2NR5R6, —COOR7, —SO3R7, —PR72 and/or —POR7R7;
• (iii) aryl or hetaryl to which may be fused further saturated or unsaturated 5- to 7-membered rings whose carbon skeleton may be interrupted by one or more —S—, —NR4—, —N═CR4—, —CR4═CR4—, —CO—, —SO— and/or —SO2— moieties, where the entire ring system may be mono- or polysubstituted by:
• C1-C18-alkyl, C1-C12-alkoxy, C1-C6-alkylthio, —C≡CR4, —CR4═CR42, hydroxyl, mercapto, halogen, cyano, nitro, —NR9R10, —NR5COR6, —CONR5R6, —SO2NR5R6, —COOR7, —SO3R7, —PR72, —POR7R7, (het)aryl, (het)aryloxy and/or (het)arylthio, where the (het)aryl radicals may each be mono- or polysubstituted by C1-C18-alkyl, C1-C12-alkoxy, C1-C6-alkylthio, hydroxyl, mercapto, halogen, cyano, nitro, —NR9R10, —NR5COR6, —CONR5R6, —SO2NR5R6, —COOR7, —SO3R7, —PR72 and/or —POR7R7;
• (iv) a —U-aryl radical which may be mono- or polysubstituted by the above radicals specified as substituents for the aryl radicals (iii), where U is an —O—, —S—, —NR4—, —CO—, —SO— or —SO2— moiety;
• (v) C1-C12-alkoxy, C1-C6-alkylthio, —C≡CR4, —CR4═CR42, hydroxyl, mercapto, halogen, cyano, nitro, —NR9R10, —NR5COR6, —CONR5R6, —SO2NR5R6, —COOR7, —SO3R7, —PR72 and/or —POR7R7;
• P is an amino radical —NR1R2;
• B is C1-C6-alkylene, phenylene or combinations of these bridging members, where the phenylene radicals may be mono- or polysubstituted by C1-C12-alkyl, nitro, cyano and/or halogen;
• A is —COOM, —SO3M or —PO3M2;
• D is phenylene, naphthylene or pyridylene, each of which may be mono- or polysubstituted by C1-C12-alkyl, C1-C6-alkoxy, hydroxyl, nitro and/or halogen;
• M is hydrogen, monovalent or divalent metal cation, especially alkaline earth metal or alkali metal cation, ammonium salts of cyclic amines, guanidinium salts or [NR5]4+;
• L is a chemical bond or an arylene or hetarylene radical, bonded to the rylene skeleton directly or via ethenylene or ethynylene, of the formulae
• —Ar— Ar-E-Ar—
• in which the (het)arylene radicals Ar may be the same or different, may comprise heteroatoms as ring atoms and/or may have fused saturated or unsaturated 5- to 7-membered rings which may likewise comprise heteroatoms, where the entire ring system may be mono- or polysubstituted by phenyl, C1-C12-alkyl, C1-C12-alkoxy, C1-C12-alkylthio and/or —NR5R6;
• E is a chemical bond or an —O—, —S—, —NR4—, —C≡C—, —CR4═CR4— or C1-C6-alkylene moiety;
• R1, R2 are each independently one of the alkyl radicals (i), cycloalkyl radicals (ii) or (het)aryl radicals (iii) specified as substituents for the R radicals;
• joined together to form a saturated or unsaturated, 5- to 7-membered ring which comprises the nitrogen atom and whose carbon chain may be interrupted by one or more —O—, —S— and/or —NR4— moieties, to which may be fused one or two unsaturated or saturated 4- to 8-membered rings whose carbon chain may likewise be interrupted by these moieties and/or —N═, where the entire ring system may be mono- or polysubstituted by:
• C1-C24-alkyl which may be substituted by C1-C18-alkoxy, C1-C18-alkylthio and/or —NR5R6, (het)aryl which may be mono- or polysubstituted by C1-C18-alkyl and/or the aforementioned radicals as substituents for alkyl, C1-C18-alkoxy, C1-C18-alkylthio and/or —NR5R6;
• Z is —O— or —S—;
• R3 is one of the alkyl radicals (i) or (het)aryl radicals (iii) specified as substituents for the R radicals;
• R′ is hydrogen;
• C1-C30-alkyl whose carbon chain may be interrupted by one or more —O—, —S—, —NR4—, —N═CR4—, —C≡C—, —CR4═CR4—, —CO—, —SO— and/or —SO2— moieties and which may be mono- or polysubstituted by the (ii), (iii), (iv) and/or (v) radicals specified as substituents for the R radicals;
• C3-C8-cycloalkyl to which may be fused further saturated or unsaturated 5- to 7-membered rings whose carbon skeleton may be interrupted by one or more —O—, —S—, —NR4—, —N═CR4—, —CR4═CR4—, —CO—, —SO— and/or —SO2— moieties, where the entire ring system may be mono- or polysubstituted by the (i), (ii), (iii), (iv) and/or (v) radicals specified as substituents for the R radicals;
• aryl or hetaryl to which may be fused further saturated or unsaturated 5- to 7-membered rings whose carbon skeleton may be interrupted by one or more —O—, —S—, —NR4—, —N═CR4—, —CR4═CR4—, —CO—, —SO— and/or —SO2— moieties, where the entire ring system may be mono- or polysubstituted by the (i), (ii), (iii), (iv), (v) radicals specified as substituents for the R radicals, and/or aryl- and/or hetarylazo, each of which may be substituted by C1-C10-alkyl, C1-C6-alkoxy and/or cyano;
• R4 is hydrogen or C1-C18-alkyl, where the R4 radicals may be the same or different when they occur more than once;
• R5, R6 are each independently:
• hydrogen;
• C1-C18-alkyl whose carbon chain may be interrupted by one or more —O—, —S—, —CO—, —SO— and/or —SO2— moieties and which may be mono- or polysubstituted by C1-C12-alkoxy, C1-C6-alkylthio, hydroxyl, mercapto, halogen, cyano, nitro and/or —COOR8;
• aryl or hetaryl to each of which may be fused further saturated or unsaturated 5- to 7-membered rings whose carbon skeleton may be interrupted by one or more —O—, —S—, —CO— and/or —SO2— moieties, where the entire ring system may be mono- or polysubstituted by C1-C12-alkyl and/or the above radicals specified as substituents for alkyl;
• where the R5 radicals may be the same or different when they occur more than once;
• R7 is C1-C18-alkyl whose carbon chain may be interrupted by one or more —O—, —S—, —CO—, —SO— and/or —SO2— moieties and which may be mono- or polysubstituted by C1-C12-alkoxy, C1-C6-alkylthio, hydroxyl, mercapto, halogen, cyano, nitro and/or —COOR8;
• aryl or hetaryl to each of which may be fused further saturated or unsaturated 5- to 7-membered rings whose carbon skeleton may be interrupted by one or more —O—, —S—, —CO— and/or —SO2— moieties, where the entire ring system may be mono- or polysubstituted by C1-C12-alkyl and/or the above radicals specified as substituents for alkyl;
• where the R7 radicals may be the same or different when they occur more than once;
• R8 is C1-C18-alkyl;
• R9, R10 are each C1-C30-alkyl whose carbon chain may be interrupted by one or more —O—, —S—, —NR4—, —N═CR4—, —C≡C—, —CR4═CR4—, —CO—, —SO— and/or —SO2-moieties and which may be mono- or polysubstituted by:
• C1-C12-alkoxy, C1-C6-alkylthio, —C≡CR4, —CR4═CR42, hydroxyl, —NR5R6, —NR5COR6, (het)aryl and/or saturated or unsaturated C4-C7-cycloalkyl whose carbon skeleton may be interrupted by one or more —O—, —S—, —NR4—, —N═CR4— and/or —CR4═CR4 moieties, where the (het)aryl and cycloalkyl radicals may each be mono- or polysubstituted by C1-C18-alkyl and/or the above radicals specified as substituents for alkyl;
• aryl or hetaryl to which may be fused further saturated or unsaturated 5- to 7-membered rings whose carbon skeleton may be interrupted by one or more —O—, —S—, —NR4—, —N═CR4—, —CR4═CR4—, —CO—, —SO— and/or —SO2— moieties, where the entire ring system may be mono- or polysubstituted by:
• C1-C18-alkyl, C1-C12-alkoxy, C1-C6-alkylthio, —C≡CR4, —CR4═CR42, hydroxyl, —NR5R6, —NR5COR6, (het)aryl, (het)aryloxy and/or (het)arylthio, where the (het)aryl radicals may be mono- or polysubstituted by C1-C18-alkyl, C1-C12-alkoxy, hydroxyl, —NR5R6 and/or —NR5COR6;
• joined to the nitrogen atom to form a saturated or unsaturated, 5- to 7-membered ring whose carbon chain may be interrupted by one or more —O—, —S— and/or —NR4— moieties, to which may be fused one or two unsaturated or saturated 4- to 8-membered rings whose carbon chain may likewise be interrupted by these moieties and/or —N═, where the entire ring system may be mono- or polysubstituted by:
• C1-C24-alkyl which may be substituted by C1-C18-alkoxy, C1-C18-alkylthio and/or —NR5R6, (het)aryl which may be mono- or polysubstituted by C1-C18-alkyl and/or the above radicals specified as substituents for alkyl, C1-C18-alkoxy, C1-C18-alkylthio and/or —NR5R6;
• m is 0, 1 or 2;
• n is 0, 2 or 4 when m=0;
• is 0, 2 or 4 when m=1;
• is 0, 4 or 6 when m=2;
• p is 0, 2 or 4 when m=0, where n+p=2 or 4 or may also be 0 when one of the two Y radicals is a radical of the formula (y1) or (y2) and the other radical is hydrogen, where at least one of the two R1 or R2 radicals in the (y1) radical is one of the (het)aryl radicals (iii) specified as substituents for the R radicals when L is a chemical bond;
• is 0, 2 or 4 when m=1, where n+p=0, 2 or 4;
• is 0, 4 or 6 when m=2, where n+p=0, 4 or 6.