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

Patent metadata

Field	Value
Publication number	US-9831042-B2
Application number	US-201614992761-A
Country	US
Kind code	B2
Filing date	Jan 11, 2016
Priority date	Jul 4, 2012
Publication date	Nov 28, 2017
Grant date	Nov 28, 2017

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.

First claim

The invention claimed is:

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 rin

Assignees

• Basf Se

Inventors

• Bruder Ingmar
• Send Robert
• Urnikaite Simona
• Malinauskas Tadas
• Daskeviciene Maryte
• Getautis Vytautas

Classifications

• C09B26/02

  Hydrazone dyes (hydrazone-azo dyes C09B56/18) · CPC title

• H01G9/2059 Primary

  comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution · CPC title

• Y02E10/549

  Organic PV cells · CPC title

• Y02E10/542

  Dye sensitized solar cells · CPC title

• C07D417/12

  linked by a chain containing hetero atoms as chain links · CPC title