ORGANIC DYES COMPRISING A HYDRAZONE MOIETY AND THEIR USE IN DYE-SENSITIZED SOLAR CELLS

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: