Organic dyes comprising a hydrazone moiety and their use in dye-sensitized solar cells

Abstract

The present invention relates to compounds of general formula I wherein R 100 and R 200 are each independently hydrogen, C 1 -C 10 -alkyl which in case of C 2 -alkyl may be interrupted by one and in case of C 3 -C 10 -alkyl by one or two nonadjacent oxygen atoms, C 5 -C 7 -cycloalkyl, aryl, aryl-C 1 -C 10 -alkyl or aryloxy-C 1 -C 10 -alkyl, D is an m-valent (m=1, 2 or 3) donor moiety which comprises at least one carbon-carbon or carbon-heteroatom double bond and/or at least one unfused or fused carbo- or heterocyclic ring, A is an acceptor moiety which comprises at least one carbon-carbon or carbon-heteroatom double bond and/or at least one unfused or fused carbo- or heterocyclic ring, and the donor moiety D and the acceptor moiety A are π-conjugated to one another. Furthermore, the present invention relates to the use of compounds of formula I for producing dye-sensitized solar cells and to dye-sensitized solar cells comprising compounds of formula I.

1 . A compound of formula I: 
       
         
           
           
               
               
           
         
         wherein:
 R 100  and R 200  are each independently hydrogen, C 1 -C 10 -alkyl wherein in case of C 2 -alkyl may be interrupted by one oxygen atom and in case of C 3 -C 10 -alkyl by one or two nonadjacent oxygen atoms, C 5 -C 7 -cycloalkyl, aryl, aryl-C 1 -C 10 -alkyl, or aryloxy-C 1 -C 10 -alkyl; 
 D is an m-valent donor moiety which comprises at least one carbon-carbon or carbon-heteroatom double bond and/or at least one unfused or fused carbo- or heterocyclic ring; 
 A is an acceptor moiety which comprises at least one carbon-carbon or carbon-heteroatom double bond and/or at least one unfused or fused carbo- or heterocyclic ring; 
 m is 1, 2, or 3; and 
 the donor moiety D and the acceptor moiety A are π-conjugated to one another. 
 
       
     
     
         2 . The compound of  claim 1 , wherein, in formula I:
 R 100  is hydrogen or C 1 -C 4 -alkyl and   R 200  is aryl or C 1 -C 10 -alkyl wherein in case of C 2 -alkyl may be interrupted by one oxygen atom and in case of C 3 -C 10 -alkyl by one or two nonadjacent oxygen atoms.   
     
     
         3 . The compound of  claim 1 , wherein, in formula I:
 m is 1; and   D is selected from the group consisting of:   
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         wherein:
 R 110 , R 120 , and R 130  are each independently hydrogen, halogen, hydroxyl, C 1 -C 10 -alkyl wherein in case of C 2 -alkyl may be interrupted by one oxygen atom and in case of C 3 -C 10 -alkyl by one or two nonadjacent oxygen atoms, C 5 -C 7 -cycloalkyl, C 1 -C 10 -alkoxy, C 1 -C 10 -alkylamino, di(C 1 -C 10 -alkyl)amino, C 1 -C 10 -alkylamino- or di(C 1 -C 10 -alkyl)aminosulfonylamino, C 1 -C 10 -alkylsulfonylamino, aryl, aryl-C 1 -C 10 -alkyl, aryloxy-C 1 -C 10 -alkyl or an —NHCOR 170  or —NHCOOR 170  radical, wherein R 170  is aryl, aryl-C 1 -C 10 -alkyl aryloxy-C 1 -C 10 -alkyl or C 1 -C 10 -alkyl wherein in case of C 2 -alkyl may be interrupted by one oxygen atom and in case of C 3 -C 10 -alkyl by one or two nonadjacent oxygen atoms; 
 R 140 , R 150 , and R 160  are each independently hydrogen, C 1 -C 10 -alkyl wherein which in case of C 2 -alkyl may be interrupted by one oxygen atom and in case of C 3 -C 10 -alkyl by one or two nonadjacent oxygen atoms, C 5 -C 7 -cycloalkyl, aryl aryl-C 1 -C 10 -alkyl, aryloxy-C 1 -C 10 -alkyl or in case R 140  and R 160  or R 50  and R 160  are bonded to adjacent carbon atoms these pairs of groups may together with the carbon atoms to which they are bonded form a five- or six-membered ring in which one CH 2  group may be replaced by an oxygen atom; 
 R 210 , R 220 , R 230 , and R 240  are each independently aryl, aryl-C 1 -C 10 -alkyl, aryloxy-C 1 -C 10 -alkyl, C 1 -C 10 -alkyl wherein in case of C 2 -alkyl may be interrupted by one oxygen atom and in case of C 3 -C 10 -alkyl by one or two nonadjacent oxygen atoms, C 5 -C 10 -cycloalkyl, or R 210  and R 220  and/or R 230  and R 240  form, together with the nitrogen atom to which they are bonded, a five- or six-membered ring in which one CH 2  group not adjacent to the nitrogen atom may be replaced by an oxygen atom, or in case NR 210 R 220  and R 110  are bonded to adjacent carbon atoms, R 110  and R 210  or R 110  and R 220 -together with the nitrogen atom of the moiety NR 210 R 220  and the carbon atom to which the moieties NR 210 R 220  and R 110  are bonded-form a five- or six-membered ring in which one CH 2  group not adjacent to the nitrogen atom may be replaced by an oxygen atom and which five- or six-membered ring may be fused to another five- or six-membered saturated or unsaturated ring; 
 R 250  and R 260  are each independently C 1 -C 10 -alkyl wherein in case of C 2 -alkyl may be interrupted by one oxygen atom and in case of C 3 -C 10 -alkyl by one or two nonadjacent oxygen atoms, C 5 -C 7 -cycloalkyl, aryl, aryl-C 1 -C 10 -alkyl or aryloxy-C 1 -C 10 -alkyl; and 
 Z is O or S. 
 
       
     
     
         4 . The compound of  claim 1 , wherein in formula I:
 m is 1; and   D is selected from the group consisting of:   
       
         
           
           
               
               
           
         
         wherein:
 R 110 , R 120 , and R 130  are each independently hydrogen, halogen, hydroxyl, C 1 -C 10 -alkyl wherein in case of C 2 -alkyl may be interrupted by one oxygen atom and in case of C 3 -C 10 -alkyl by one or two nonadjacent oxygen atoms, C 5 -C 7 -cycloalkyl, C 1 -C 10 -alkoxy, C 1 -C 10 -alkylamino, di(C 1 -C 10 -alkyl)amino, C 1 -C 10 -alkylamino- or di(C 1 -C 10 -alkyl)aminosulfonylamino, C 1 -C 10 -alkylsulfonylamino, aryl, aryl-C 1 -C 10 -alkyl, aryloxy-C 1 -C 10 -alkyl or an —NHCOR 170  or —NHCOOR 170  radical, wherein R 170  is aryl, aryl-C 1 -C 10 -alkyl, aryloxy-C 1 -C 10 -alkyl or C 1 -C 10 -alkyl wherein in case of C 2 -alkyl may be interrupted by one oxygen atom and in case of C 3 -C 10 -alkyl by one or two nonadjacent oxygen atoms; 
 R 140 , R 150 , and R 160  are each independently hydrogen, C 1 -C 10 -alkyl wherein in case of C 2 -alkyl may be interrupted by one oxygen atom and in case of C 3 -C 10 -alkyl by one or two nonadjacent oxygen atoms, C 5 -C 7 -cycloalkyl, aryl aryl-C 1 -C 10 -alkyl, aryloxy-C 1 -C 10 -alkyl or in case R 140  and R 160  or R 150  and R 160  are bonded to adjacent carbon atoms these pairs of groups may together with the carbon atoms to which they are bonded form a five- or six-membered ring in which one CH 2  group may be replaced by an oxygen atom; 
 R 210 , R 220 , R 230 , and R 240  are each independently aryl, aryl-C 1 -C 10 -alkyl, aryloxy-C 1 -C 10 -alkyl, C 1 -C 10 -alkyl wherein in case of C 2 -alkyl may be interrupted by one oxygen atom and in case of C 3 -C 10 -alkyl by one or two nonadjacent oxygen atoms, C 5 -C 10 -cycloalkyl, or R 210  and R 220  and/or R 230  and R 240  form, together with the nitrogen atom to which they are bonded, a five- or six-membered ring in which one CH 2  group not adjacent to the nitrogen atom may be replaced by an oxygen atom, or in case NR 210 R 220  and R 110  are bonded to adjacent carbon atoms, R 110  and R 210  or R 110  and R 220 -together with the nitrogen atom of the moiety NR 210 R 220  and the carbon atom to which the moieties NR 210 R 220  and R 110  are bonded-form a five- or six-membered ring in which one CH 2  group not adjacent to the nitrogen atom may be replaced by an oxygen atom and which five- or six-membered ring may be fused to another five- or six-membered saturated or unsaturated ring; 
 R 250  is C 1 -C 10 -alkyl wherein in case of C 2 -alkyl may be interrupted by one oxygen atom and in case of C 3 -C 10 -alkyl by one or two nonadjacent oxygen atoms, C 5 -C 7 -cycloalkyl, aryl, aryl-C 1 -C 10 -alkyl or aryloxy-C 1 -C 10 -alkyl; and 
 
         Z is O or S. 
       
     
     
         5 . The compound of  claim 1 , wherein in formula I:
 m is 1; and   D is a moiety:   
       
         
           
           
               
               
           
         
         wherein:
 R 110  is hydrogen, halogen, hydroxyl, C 1 -C 10 -alkyl wherein in case of C 2 -alkyl may be interrupted by one oxygen atom and in case of C 3 -C 10 -alkyl by one or two nonadjacent oxygen atoms, C 5 -C 7 -cycloalkyl, C 1 -C 10 -alkoxy, C 1 -C 10 -alkylamino, di(C 1 -C 10 -alkyl)amino, C 1 -C 10 -alkylamino- or di(C 1 -C 10 -alkyl)aminosulfonylamino, C 1 -C 10 -alkylsulfonylamino, aryl, aryl-C 1 -C 10 -alkyl, aryloxy-C 1 -C 10 -alkyl or an —NHCOR 170  or —NHCOOR 170  radical, wherein R 170  is aryl, aryl-C 1 -C 10 -alkyl, aryloxy-C 1 -C 10 -alkyl or C 1 -C 10 -alkyl wherein in case of C 2 -alkyl may be interrupted by one oxygen atom and in case of C 3 -C 10 -alkyl by one or two nonadjacent oxygen atoms, and 
 R 210  and R 220  are each independently aryl, aryl-C 1 -C 10 -alkyl, aryloxy-C 1 -C 10 -alkyl, C 1 -C 10 -alkyl wherein in case of C 2 -alkyl may be interrupted by one oxygen atom and in case of C 3 -C 10 -alkyl by one or two nonadjacent oxygen atoms, C 5 -C 10 -cycloalkyl, or R 210  and R 220  form, together with the nitrogen atom to which they are bonded, a five- or six-membered ring in which one CH 2  group not adjacent to the nitrogen atom may be replaced by an oxygen atom, or in case NR 210 R 220  and R 110  are bonded to adjacent carbon atoms, R 110  and R 210  or R 110  and R 220 -together with the nitrogen atom of the moiety NR 210 R 220  and the carbon atom to which the moieties NR 210 R 220  and R 110  are bonded-form a five- or six-membered ring in which one CH 2  group not adjacent to the nitrogen atom may be replaced by an oxygen atom and which five- or six-membered ring may be fused to another five- or six-membered saturated or unsaturated ring. 
 
       
     
     
         6 . The compound of  claim 1 , wherein, in formula I, A is a group of formula Ia: 
       
         
           
           
               
               
           
         
         wherein A* is a moiety selected from the group consisting of: 
       
       
         
           
           
               
               
           
         
         wherein:
 * indicates the position which the double bond of the group of formula Ia is bonded to; 
 R 310  and R 320  are each independently hydrogen, C 1 -C 10 -alkyl wherein in case of C 2 -alkyl may be interrupted by one oxygen atom and in case of C 3 -C 10 -alkyl by one or two nonadjacent oxygen atoms, or C 5 -C 7 -cycloalkyl; 
 R 330  is hydrogen, C 1 -C 10 -alkyl wherein in case of C 2 -alkyl may be interrupted by one oxygen atom and in case of C 3 -C 10 -alkyl by one or two nonadjacent oxygen atoms, partly fluorinated C 1 -C 10 -alkyl, perfluorinated C 1 -C 10 -alkyl, C 5 -C 7 -cycloalkyl, aryl, aryl-C 1 -C 10 -alkyl or aryloxy-C 1 -C 10 -alkyl; 
 R 340  is hydrogen, NO 2 , CN, COR 350 , COOR 350 , SO 2 R 350  or SO 3 R 350 , wherein R 350  is aryl, aryl-C 1 -C 10 -alkyl, aryloxy-C 1 -C 10 -alkyl or C 1 -C 10 -alkyl which in case of C 2 -alkyl may be interrupted by one and in case of C 3 -C 10 -alkyl by one or two nonadjacent oxygen atoms; 
 R 410  is hydrogen, C 1 -C 10 -alkyl wherein in case of C 2 -alkyl may be interrupted by one oxygen atom and in case of C 3 -C 10 -alkyl by one or two nonadjacent oxygen atoms and which may be mono- or polysubstituted by hydroxyl, mercapto, halogen, cyano, nitro, —COOM and/or —COOR 420 , C 5 -C 7 -cycloalkyl, aryl, aryl-C 1 -C 10 -alkyl, aryloxy-C 1 -C 10 -alkyl, or an —NHCOR 420  or —N(CO R 420 ) 2  radical where the two R 420  in the latter may be the same or different; 
 X is independently CH or N; 
 Y is O, C(CN) 2 , C(CN)(COOM) or C(CN)(COOR 420 ); 
 M is alkali metal cation or [NR 420 ] 4   + ; and 
 R 420  is hydrogen, aryl, aryl-C 1 -C 10 -alkyl, aryloxy-C 1 -C 10 -alkyl or C 1 -C 10 -alkyl wherein in case of C 2 -alkyl may be interrupted by one oxygen atom and in case of C 3 -C 10 -alkyl by one or two nonadjacent oxygen atoms. 
 
       
     
     
         7 . The compound of  claim 1 , wherein, in formula I, A is: 
       
         
           
           
               
               
           
         
         wherein:
 R 340  is hydrogen, NO 2 , CN, COR 350 , COOR 350 , SO 2 R 350  or SO 3 R 350 , wherein R 350  is aryl, aryl-C 1 -C 10 -alkyl, aryloxy-C 1 -C 10 -alkyl or C 1 -C 10 -alkyl wherein in case of C 2 -alkyl may be interrupted by one oxygen atom and in case of C 3 -C 10 -alkyl by one or two nonadjacent oxygen atoms 
 R 410  is hydrogen, C 1 -C 10 -alkyl wherein in case of C 2 -alkyl may be interrupted by one oxygen atom and in case of C 3 -C 10 -alkyl by one or two nonadjacent oxygen atoms and which may be mono- or polysubstituted by hydroxyl, mercapto, halogen, cyano, nitro, —COOM and/or —COOR 420 , C 5 -C 7 -cycloalkyl, aryl, aryl-C 1 -C 10 -alkyl, aryloxy-C 1 -C 10 -alkyl, or an —NHCOR 420  or —N(CO R 420 ) 2  radical where the two R 420  in the latter may be the same or different, 
 M is alkali metal cation or [NR 420 ] 4   + ; and 
 R 420  is hydrogen, aryl, aryl-C 1 -C 10 -alkyl, aryloxy-C 1 -C 10 -alkyl or C 1 -C 10 -alkyl wherein in case of C 2 -alkyl may be interrupted by one oxygen atom and in case of C 3 -C 10 -alkyl by one or two nonadjacent oxygen atoms. 
 
       
     
     
         8 . The compound of  claim 1 , wherein, in formula I, A is: 
       
         
           
           
               
               
           
         
         wherein:
 R 340  is hydrogen, NO 2 , CN, COR 350 , COOR 350 , SO 2 R 350  or SO 3 R 350 ; 
 R 350  is aryl, aryl-C 1 -C 10 -alkyl, aryloxy-C 1 -C 10 -alkyl or C 1 -C 10 -alkyl wherein in case of C 2 -alkyl may be interrupted by one oxygen atom and in case of C 3 -C 10 -alkyl by one or two nonadjacent oxygen atoms; 
 R 410  is aryl or C 1 -C 10 -alkyl which in case of C 2 -alkyl may be interrupted by one and in case of C 3 -C 10 -alkyl by one or two nonadjacent oxygen atoms and which is terminally substituted by hydroxyl, —COOM or —COOR 420 ; 
 M is alkali metal cation or [NR 420 ] 4   + ; and 
 R 420  is hydrogen or C 1 -C 10 -alkyl wherein in case of C 2 -alkyl may be interrupted by one oxygen atom and in case of C 3 -C 10 -alkyl by one or two nonadjacent oxygen atoms. 
 
       
     
     
         9 . (canceled) 
     
     
         10 . A dye-sensitized solar cell, comprising a compound of formula I according to  claim 1 . 
     
     
         11 . The compound of  claim 1 , wherein, in formula I:
 m is 2; and   D is selected from the group consisting of:   
       
         
           
           
               
               
           
         
         wherein R 170  is aryl, aryl-C 1 -C 10 -alkyl, aryloxy-C 1 -C 10 -alkyl, or C 1 -C 10 -alkyl wherein in case of C 2 -alkyl may be interrupted by one oxygen atom and in case of C 3 -C 10 -alkyl by one or two nonadjacent oxygen atoms, and wherein in case of two moities R 170  may vary independently of each other. 
       
     
     
         12 . The compound of  claim 1 , wherein, in formula I:
 m is 2; and   D is selected from the group consisting of:   
       
         
           
           
               
               
           
         
         wherein R 170  is aryl, aryl-C 1 -C 10 -alkyl, aryloxy-C 1 -C 10 -alkyl, or C 1 -C 10 -alkyl wherein in case of C 2 -alkyl may be interrupted by one oxygen atom. 
       
     
     
         13 . The compound of  claim 1 , wherein, in formula I:
 m is 2; and   D is selected from the group consisting of:   
       
         
           
           
               
               
           
         
         wherein R 170  is aryl, aryl-C 1 -C 10 -alkyl, aryloxy-C 1 -C 10 -alkyl, or C 1 -C 10 -alkyl wherein in case of C 2 -alkyl may be interrupted by one oxygen atom and in case of C 3 -C 10 -alkyl by one or two nonadjacent oxygen atoms. 
       
     
     
         14 . The compound of  claim 1 , wherein, in formula I:
 m is 3; and   D is selected from the group consisting of:   
       
         
           
           
               
               
           
         
         wherein R 170  is aryl, aryl-C 1 -C 10 -alkyl, aryloxy-C 1 -C 10 -alkyl, or C 1 -C 10 -alkyl wherein in case of C 2 -alkyl may be interrupted by one oxygen atom and in case of C 3 -C 10 -alkyl by one or two nonadjacent oxygen atoms. 
       
     
     
         15 . The compound of  claim 1 , wherein, in formula I:
 m is 3; and   D is selected from the group consisting of:   
       
         
           
           
               
               
           
         
       
     
     
         16 . The compound of  claim 1 , wherein, in formula I:
 m is 3; and   D is a moiety: