Dye comprising a chromophore to which an acyloin group is attached

Abstract

The present invention relates to a dye comprising a chromophore to which an acyloin group as anchoring group is attached, to a method of synthesis of such dye, to an electronic device comprising such dye and to the use of such dye.

1 . A dye, comprising a chromophore to which an acyloin group is attached, and represented by formula (1a) or (1b): 
       
         
           
           
               
               
           
         
         wherein said chromophore is an organic or metal-organic compound absorbing electromagnetic radiation in a range from 300-1200 nm, or 
         wherein A is selected from the group consisting of H, a cyclic alkyl, an acyclic alkyl, a straight or branched chain moiety of formula —(CH 2 ) n1 —R, —[(CR═CR) n1 —(CH 2 ) n2 ] p —R, —[(C≡C) n1 —(CH 2 ) n2 ] p —R, —[(CH 2 ) n1 —X n2 ] p —R, a halogen, moiety comprising at least one heteroatom, a substituted phenyl, an un-substituted phenyl, a substituted biphenyl, an unsubstituted biphenyl, a substituted heteroaryl, an unsubstituted heteroaryl, and a moiety forming a ring structure with said acyloin group, 
         wherein, at each occurrence and independently, n1 and n2=0-12, p=0-6, 
         wherein X is —CR 2 , O, S, NR, —CR, 
         wherein R is selected from the group consisting of H, a straight or branched alkyl chain of formula —C n H 2n+1 , —COOR 1 , —OR 1 , —SR 1 , —NR 1   2 , F, Cl, Br, I, O, N, NO 2 , CN, and CF 3 , wherein R 1  is H or a straight or branched alkyl chain of formula —C n H 2n+1 , or a substituted or non-substituted phenyl or biphenyl, heteroaryl, and n=0-12. 
       
     
     
         2 . The dye of  claim 1 , represented by formula (2a), (2b), (2c), (2d), (2e), (2f), (2g), (2h), (2i), or (2j) 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         wherein Y, at each occurrence, is independently —CR 2 , O, S, NR, or —CR. 
       
     
     
         3 . The dye of  claim 2 , represented by formula 2d, 2e, 2f, or 2h. 
     
     
         4 . The dye of  claim 1 , wherein said chromophore is selected from the group consisting of moieties shown in group 3 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         or any combination of the moieties of group 3, wherein said chromophore is linked to said acycloin group by any of the C-atoms or X or Y or R within said chromophore, wherein Z is one or more moieties which, at each occurrence, is independently selected from the group consisting of H, a cyclic alkyl, an acyclic alkyl, a straight or branched chain moiety of formula —(CH 2 ) n1 —R, —[(CR═CR) n1 —(CH 2 ) n2 ] p —R, —[(C≡C) n1 —(CH 2 ) n2 ] p —R, —[(CH 2 ) n1 —X n2 ] p —R, a halogen, moiety comprising at least one heteroatom, a substituted phenyl, an unsubstituted phenyl, a substituted biphenyl, an unsubstituted biphenyl, a substituted heteroaryl, and an unsubstituted heteroaryl. 
       
     
     
         5 . The dye of  claim 4 , represented by formula (5) 
       
         
           
           
               
               
           
         
         wherein R 11 , R 12 , R 13 , at each occurrence, are independently selected from the group consisting of H, a straight or branched alkyl chain of formula —C n H 2n+1 , —COOR 1 , —OR 1 , —SR 1 , —NR 1   2 , F, Cl, Br, I, O, N, NO 2 , CN, CF 3 , wherein R 1  is H or any straight or branched alkyl chain of formula —C n H 2n+ , or any substituted or non-substituted phenyl or biphenyl, heteroaryl, n=0-12. 
       
     
     
         6 . The dye of  claim 5 , represented by formula (6) 
       
         
           
           
               
               
           
         
         or represented by any of structures 17-26: 
       
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
     
     
         7 . The dye of  claim 5 , represented by formula (7), (8), (9), (10), (11), (12), or (13): 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
     
     
         8 . The dye of  claim 1 , wherein said chromophore is a metal complex selected from the group consisting of u structures represented by formula (14)
   (L) n3 (L′) n4 M(Hal) n5   (14),
   wherein   M is Ruthenium Ru, Osmium Os, or Iridium Ir,   Hal is independently Cl, Br, I, CN, or —NCS,   n3, n4, and n5 are integers which, at each occurrence, are independently 0-4,   and L and L′ are organic heterocyclic ligands comprising nitrogen atoms which are linked by N-atoms to the respective metal M, and wherein either one of L and L′, or both L and L′ are linked to the acyloin group by any of the C-atoms within said ligands.   
     
     
         9 . The dye of  claim 8 , wherein said ligands L and L′ are independently, at each occurrence, mono- or polycyclic, condensed rings or such rings covalently bonded to each other. 
     
     
         10 . The dye of  claim 8 , wherein said ligands L and L′ are independently, at each occurrence, selected from the group consisting of 
       
         
           
           
               
               
           
         
         wherein Z is one or more moieties which, at each occurrence, is independently selected from the group consisting of H, a cyclic alkyl, an acyclic alkyl, a straight or branched chain moiety of formula —(CH 2 ) n1 —R, —[(CR═CR) n1 —(CH 2 ) n2 ] p —R, —[(C≡C) n1 —(CH 2 ) n2 ] p —R, —[(CH 2 ) n1 —X n2 ] p —R, a halogen, a moiety comprising at least one heteroatom, a substituted phenyl, an unsubstituted phenyl, a substituted biphenyl, an unsubstituted biphenyl, a substituted heteroaryl, and an unsubstituted heteroaryl. 
       
     
     
         11 . The dye of  claim 1 ,
 wherein said chromophore is a metal complex represented by formula (16),
   (IL″) n6 M′  (16),
 
   wherein   M′ is Palladium Pd, Platinum Pt or Nickel Ni,   n6 being is an integer 0-4,   and L″ is an organic heterocyclic ligand comprising at least one nitrogen atom, said ligand being linked by one or several of said N-atoms to the respective metal M′, and said ligand being linked to said acycloin group by any of the C-atoms within said ligand.   
     
     
         12 . The dye of  claim 11 , wherein said ligand L″ is selected from the group consisting of 
       
         
           
           
               
               
           
         
         wherein Z is one or more moieties which, at each occurrence, is independently selected from the group consisting of H, a cyclic alkyl, an acyclic alkyl, a straight or branched chain moiety of formula —(CH 2 ) n1 —R, —[(CR═CR) n1 —(CH 2 ) n2 ] p —R, —[(C≡C) n1 —(CH 2 ) n2 ]—R, —[(CH 2 ) n1 —X n2 ] p —R, a halogen, a moiety comprising at least one heteroatom, a substituted phenyl, an unsubstituted phenyl, a substituted biphenyl, an unsubstituted biphenyl, a substituted heteroaryl, and an unsubstituted heteroaryl. 
       
     
     
         13 . An electronic device, comprising the dye of  claim 1 . 
     
     
         14 . The device of  claim 13 , which is a solar cell further comprising a photoactive semiconductor porous material. 
     
     
         15 . The device of  claim 13 , further comprising a charge-transporting agent which is a liquid, ionic liquid, polymer gel based, or solid state electrolyte. 
     
     
         16 . The device of  claim 14 , which is a solar cell wherein said dye is chemisorbed to said photoactive semiconductor porous material. 
     
     
         17 . The device of  claim 13 , further comprising at least one other dye. 
     
     
         18 . The device according to  claim 17 , wherein said at least one other dye is represented by formula (1c) or (1b). 
     
     
         19 . The device of  claim 17 , wherein said at least one other dye selected from the group consisting of structures 15 and 27-32: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
     
     
         20 . The device of  claim 14 , wherein said photoactive semiconductor porous material is at least one selected from the group consisting of TiO 2 , SnO 2 , ZnO, Nb 2 O 5 , ZrO 2 , CeO 2 , WO 3 , Cr 2 O 3 , CrO 2 , CrO 3 , SiO 2 , Fe 2 O 3 , CuO, Al 2 O 3 , CuAlO 2 , SrTiO 3 , SrCu 2 O 2 , and ZrTiO 4 . 
     
     
         21 . The device of  claim 20 , wherein said photoactive semiconductor porous material has one or several of the following features:
 a thickness of 1-100 μm,   consists of one or more layers   comprises particles having an average diameter or length in a range of from 1 nm to 40 nm,   is a mixture of at least a first particle and second particle, said first particle having an average diameter or length in a range of from 1 nm to 30 nm, and said second particle having an average diameter in a range of from 30 nm to 100 nm and/or a length in a range of from 100 nm to 5 μm.   
     
     
         22 . A dye-sensitized solar cell comprising a sensitizer comprising the dye of  claim 1 . 
     
     
         23 . The dye-sensitized solar cell of  claim 22 , further comprising at least one other dye. 
     
     
         24 . The dye-sensitized solar cell of  claim 23 , wherein said at least one other dye is represented by formula (1a) or (1b) or a dye selected from structures 15, 27-32: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
     
     
         25 . A method of photocatalyzing a reaction, the method comprising:
 exposing a component of the reaction to light in the pressure of the dye of  claim 1 .   
     
     
         26 . The dye of  claim 1 , wherein the chromophore absorbs electromagnetic radiation in a range from 350-500 nm. 
     
     
         27 . The dye of  claim 1 , wherein the chromophore absorbs electromagnetic radiation in a range from 500-750 nm. 
     
     
         28 . The dye of  claim 4 , wherein at least one Z of the chromophore is a moiety of group 4: