Organic dyes comprising a hydrazone moiety and their use in dye-sensitized solar cells
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 represented by 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 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,
the donor moiety D and the acceptor moiety A are π-conjugated to one another,
when m=1 the donor moiety D is selected from the group consisting of:
R 110 , R 120 and R 130 independently hydrogen, halogen, hydroxyl, 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, 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,
R 140 , R 150 and R 160 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, 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 170 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 and in case of two moities for m=2 may vary independently of each other,
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 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 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 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,
Z is O or S,
when m=2 the donor moiety D is selected from the group consisting of:
wherein R 170 is defined above and in case of two moieties may vary independently of each other,
when m=3 the donor moiety D is selected from the group consisting of:
wherein R 170 is defined above,
A is represented by formula (Ia):
A* represents a moiety selected from the group consisting of:
* 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 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, or C 5 -C 7 -cycloalkyl,
R 330 is 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, 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 ,
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 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 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(COR 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 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.
2. The compound of claim 1 , wherein
R 100 is hydrogen or C 1 -C 4 -alkyl, and
R 200 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.
3. The compound of claim 1 , wherein
when m=1 the donor moiety D is selected from the group consisting of:
R 110 , R 120 and R 130 are each independently hydrogen, halogen, hydroxyl, 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, 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,
R 140 , R 150 and R 160 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, 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 170 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 and in case of two moities for m=2 may vary independently of each other,
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 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 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 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,
Z is O or S,
when m=2 the donor moiety D is selected from the group consisting of:
wherein R 170 is defined above and in case of two moities may vary independently of each other, and
when m=3 the donor moiety D is selected from the group consisting of:
wherein R 170 is defined above.
4. The compound of claim 1 , wherein
when m=1 the donor moiety D is selected from the group consisting of:
when for m=2 the donor moiety D is selected from the group consisting of:
and
when m=3 the donor moiety D is selected from the group consisting of:
5. The compound of claim 1 , wherein
when m=1 the donor moiety D is a represented by formula (D01):
R 110 is hydrogen, halogen, hydroxyl, 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, 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,
R 170 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 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 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 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,
when m=2 the donor moiety D is selected from the group consisting of:
wherein R 170 is defined above, and
when m=3 the donor moiety D is represented by the formula:
6. The compound of claim 1 , wherein the acceptor moiety A is: represented by the formula (A01):
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 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 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 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(COR 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 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.
7. The compound of claim 1 , wherein the acceptor moiety A is represented by the formula (A01):
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 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 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 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.
8. The compound of claim 1 , wherein m is 1.
9. The compound of claim 1 , wherein m is 2.
10. The compound of claim 1 , wherein m is 3.
11. A dye-sensitized solar cell comprising the compound of claim 1 .
12. A method of producing a dye-sensitized solar cell comprising incorporating the compound of claim 1 into a dye-sensitized solar cell.