Electrochromic compounds

Abstract

The invention concerns electrochromic compounds of the general formula I. These compounds may be used in electrochromic devices, especially electrochromic devices comprising nanostructured films.

1 . A compound of the general formula I 
     
       
         
         
             
             
         
       
     
     wherein R 1  is —(CH 2 ) m — wherein m is zero or an integer from 1 to 10; or aryl or heteroaryl having up to 14 carbon atoms; or branched-chain alkyl or alkenyl, or cycloalkyl, each having up to 10 carbon atoms; the aryl, heteroaryl, branched alkyl, branched alkenyl or cycloalkyl radical optionally being attached to the -P(O)(OH) 2  group via a —(CH 2 ) m — linkage, wherein n is zero or an integer from 1 to 10; it also being possible for the and, heteroaryl, branched alkyl, branched alkenyl or cycloalkyl radical to be optionally substituted by one or more of the following substituenfs which may be the same or different: lower alkyl, lower alkenyl, phenyl-lower alkyl, diphenyl-lower alkyl, phenyl, phenoxy, lower alkanoyloxy, halogen, amino, cyano, nitro, lower alkylamino, di-lower alkylamino, phenylamino, lower alkanoylamino, benzoylamino; lower alkylsulfonylamino, phenysulfonylamino, lower alkanoyl, benzoyl, carboxy, lower alkoxycarbonyl carbamoyl, N-lower alkyl carbamoyl, N,N-di-lower alkyl carbamoyl, ureido, N-lower alkylureido, lower alkylsulfonyl; phenylsulfonyl; lower alkyl which is substituted by hydroxy; lower alkoxy, amino, lower alkylamino, di-lower alkylamino, halogen, carboxy or lower alkoxycarbonyl; lower alkoxy which is substituted by hydroxy, lower alkoxy, amino, lower alkylamino, di-lower alkylamino, halogen, carboxy or lower alkoxycarbonyl; C 3 -C 7 -alkoxy; and/or bivalent methylenedioxy; it being possible for all phenyl groups mentioned as such or in composed radicals (such as benzoyl, phenylamino etc.) to be unsubstituted or substituted by lower alkyl, lower alkoxy, halogen, hydroxy and/or nitro; and R 2  is R 3 R 4  wherein R 3  is —(CH 2 ) p — wherein p is zero or an integer from 1 to 10; and R 4  is —P(O)(OH) 2 ; or aryl or heteroaryl having up to 14 carbon atoms; or branched-chain alkyl or alkenyl, or cycloalkyl, each having up to 10 carbon atoms, it being possible for the aryl, heteroaryl, branched alkyl, branched alkenyl or cycloalkyl radical to be unsubstituted or substituted by one or more of the substituents given in the definition of R 1 ; and X −  is a charge-balancing ion; with the provisos that R 1  cannot be —(CH 2 ) m — wherein m is 2 or 3, when R 2  is —(CH 2 ) 2 ——P(O)(OH) 2 ; and R 1  cannot be —(CH 2 ) m — wherein m is 2, when R 2  is phenyl. 
   
   
       2 . A compound according to  claim 1 , wherein Rhub  1  is —(CH 2 ) m — wherein m is 1, 2 or 3; or phenyl which is attached to the —P(O)(OH) 2  group via —(CH 2 ) n — in the para-position of the phenyl ring, wherein n is 1 or 2; R 2  is R 3 R 4  wherein R 3  is —(CH 2 ) p — wherein p is zero, 1, 2or 3, and R 4  is unsubstituted phenyl or naphthyl, or phenyl or naphthyl which is mono-, di- or tri-substituted by C 1-4 -alkyl, halogen, cyano, nitro, phenoxy or benzoyl; and X −  is Cl − , Br − , ClO 4   −  PF 6   − , BF 4   − ; C 2 F 6 NO 4 S 2   −  or CF 3 SO 3   − , especially Cl −  or PF 6   − . 
   
   
       3 . A compound according to  claim 1 , wherein R 1  is phenyl which is attached to the —P(O)(OH) 2  group via —(CH 2 ) n — in the para-position of the phenyl ring, wherein n is 1 or 2; R 2  is R 3 R 4  wherein R 3  is —(CH 2 ) p — wherein p is zero, 1, 2 or 3 and R 4  is -P(O) (OH) 2 ; arid X −  is Cl − , Br − , ClO 4   − , PF 6   − , BF 4   − ; C 2 F 6 NO 4 S 2   −  or CF 3 S 3   − , especially Cl −  or PF 6   − . 
   
   
       4 . A compound according to  claim 1  selected from:
 (1) 1-Phosphonoethyl-1′-(3-propylphenyl)-4,4′-bipyridinium dichloride;   (2) 1-Phosphonoethyl-1′-(3-propylphenyl)-4,4′-bipyridinium bis-hexafluorophosphate;   (3) 1-Phosphonoethyl-1′-(2,4,6-trimethylphenyl)-4,4′-bipyridinium dichloride;   (4) 1-Phosphonoethyl-1′-(2,4,6-trimethylphenyl)-4,4′-bipyridimum bis-hexafluorophosphate;   (5) 1-Phosphonoethyl-1′-(naphthyl)-4,4′-bipyridinium dichloride;   (6) 1-Phosphonoethyl-1′-(4-cyanonaphthyl)-4,4′-bipyridinium dichloride;   (7) 1-Phosphonoethyl-1′-(4-methylphenyl)-4,4′-bipyridinium dichloride;   (8) 1-Phosphonoethyl-1′-(4-cyanophenyl)-4,4′-bipyridinium dichloride;   (9) 1-Phosphonoethyl-1′-(4-fluorophenyl)-4,4′-bipyridinium dichloride;   (10) 1-Phosphonoethyl-1′-(4-phenoxyphenyl)-4,4′-bipyridinium dichloride;   (11) 1-Phosphonoethyl-1′-(4-t-butylphenyl)-4,4′-bipyridinium dichloride;   (12) 1-Phosphonoethyl-1′-(2,6-dimethylphenyl)-4,4′-bipyridinium dichloride;   (13) 1-Phosphonoethyl-1′-(3,5-dimethylphenyl)-4,4′-bipyridinium dichloride;   (14) 1-Phosphonoethyl-1′-(4-benzophenone)-4,4′-bipyridinium dichloride;   (15) 1-Phosphonobenzyl-1′-(3-propylphenyl)-4,4′-bipyridinium dichloride;   (16) 1-Phosphonobenzyl-1′-(3-propylphenyl)-4,4′-bipyridinium bis-hexafluorophosphate;   (17) 1-Phosphonobenzyl-1′-(phosphonoethyl)-4,4′-bipyridinium dichloride;   (18) 1-Phosphonobenzyl-1′-(2,4-dinitrophenyl)-4,4′-bipyridimum dichloride;   (19) 1-Phosphonobenzyl-1′-(2,4-dinitrophenyl)-4,4′-bipyridinium bis-hexafluorophosphate;   (20) 1-Phosphonobenzyl-1′-(4-phenoxyphenyl)-4,4′-bipyridinium dichloride;   (21) 1-Phosphonobenzyl-1′-(4-phenoxyphenyl)-4,4′-bipyridinium bis-hexatluorophosphate;   (22) 1-Phosphonobenzyl-1′-(4-fluorophenyl)-4,4′-bipyridinium dichloride;   (23) 1-Phosphonobenzyl-1′-(4-methylphenyl)-4,4′-bipyridinium dichloride;   (24) 1-Phosphonobenzyl-1′-(2,4,6-trimethylphenyl)-4,4′-bipyridiniurn dichloride;   (25) 1-Phosphonobenzyl-1′-(benzyl)-4,4′-bi pyridinium dichloride;   (26) 1-Phosphonobenzyl-1′-(naphthyl)-4,4′-bipyridiniuni dichloride;   (27) 1-Phosphonobenzyl-1′-(phenyl)-4,4′-bipyridinium dichloride;   (28) 1-Phosphonobenzyl-1′-(4-cyanophenyl)-4,4′-bipyridinium dichloride;   (29) 1-Phosphonobenzyl-1′-(4-benzophenone)-4,4′-bipyridinium dichloride;   (30) 1-Phosphonobenzyl-1′-(4-cyanonaphthyl)-4,4′-bipyridinium dichloride;   (31) 1-Phosphonobenzyl-1′-(2,6-dimethylphenyl)-4,4′-bipyridJnium dichloride;   (32) 1-Phosphonobenzyl-1′-(3,5-dimethylphenyl)-4,4′-bipyridinium dichloride; and   (33) 1-Phosphonoethyl-1′-(2,4,6-trimethylphenyl)-4,4′-bipyridinium trifluoromethanesulfonimide.   
   
   
       5 . A process for preparing a compound of the general formula I given and defined in  claim 1 , which process comprises: (a) reacting bipyridine of the formula II 
     
       
         
         
             
             
         
       
     
     with 1-halo-2,4-dinitrobenzene, if appropriate, to form a compound of the formula III 
     
       
         
         
             
             
         
       
       (b) reacting the compound of formula II or III with a phosphony Sating agent of the formula R 1 -Y—P(O)(OR) 2  to form a compound of the formula IV 
     
     
       
         
         
             
             
         
       
       (c) reacting the compound of formula IV with 1-halo-2,4-dinitrobenzene, if appropriate, to form a compound of the formula V 
     
     
       
         
         
             
             
         
       
       (d) reacting the compound of formula IV or V with a compound of the formula R 2 -Y to form a compound of the formula VI 
     
     
       
         
         
             
             
         
       
       (e) hydtolysing the compound of formula VI to form a compound of the formula I′. 
     
     
       
         
         
             
             
         
       
     
     and if appropriate, (f) converting the compound of formula I′ to a compound of the formula I 
     
       
         
         
             
             
         
       
     
     wherein in the above formulae each R is an ester forming group which may be the same or different, Y is halogen or amino, X′ −  is halogen, preferably Br −  or Cl − , and R 1 , R 2  and X −  are as defined in  claim 1 . 
   
   
       6 . A compound of the general formula V 
     
       
         
         
             
             
         
       
     
     wherein R 1  is as defined in  claim 1  except that the provisos of  claim 1  are excluded, each R is an ester forming group which may be the same or different, and each X′ −  is independently halogen. 
   
   
       7 . A compound according to  claim 6 , wherein each R is independently methyl or ethyl; R 1  is —(CH 2 ) m — wherein m is 1, 2 or 3, or phenyl which is attached to the —P(O)(OH) 2  group via —(CH 2 ) n — in the para-position of the phenyl ring, wherein n is 1 or 2; and each X′ −  is independently Br −  or Cl − . 
   
   
       8 . A compound according to  claim 6  which is 1-diethylbenzylphosphonate-1′-(2,4-dinitrophenyl)-4,4′-bipyridinium dichloride. 
   
   
       9 . An electrode or an electrochromic device comprising a compound according to formula I. 
     
       
         
         
             
             
         
       
     
     wherein R 1 is an aryl radical or a. heteroaryl radical having up to 14 carbon atoms; the aryl radical or the heteroaryI radical optionally being attached to the —P(O)(O) 2  group via a —(CH 2 ) n — linkage, wherein n is zero or an integer from 1 to 10; wherein the aryl radical or the heteroaryl radical may be optionally substituted by one or more of the foSloxving substituents which may be the same or different; lower alkykl, lower alkenyl, phenyl-lower alkyl, diphenyl-lower alkyl phenyl phenoxy, lower alkanoyloxy, halogen, amino, eyano, nitro, lower alkylamino, di-lower alkylamino. phenylamino, lower alkanoylamino, benzoylamino; lower alkylsulfonylamino, phenysulfonylamino, lower alkanoyl, benzoyl carboxy, lower alkoxycarbonyl, carbamoyl, N-lower alkylcarbamoyl, N,N-di-lower alkylcarbamoyl, ureido, N-lower alkylureido, lower alkylsulfonyl; phenylsulfonyl; lower alkyl which is substituted by hydroxy, lower alkoxy, amino, lower alkylamino, di-lower alkyl amino, halogen, carboxy or lower alkoxycarbonyl, lower alkoxy which is substituted by hydroxy, lower alkoxy, amino, lower alkylamino, di-lower alkylamino, halogen, carboxy or lower alkoxycarbonyl; C 3 -C 7 -alkoxy; and/or bivalent methylenedioxy; wherein all phenyl groups mentioned as such or in composed radicals (such as benzoyl phenylamino etc.) may be unsubstituted or substituted by lower alkyl, lower alkoxy, halogen, hydroxy and/or nitro;
 and R 2  is R 3 R 4  wherein R 3  is —(CH 2 ) p — wherein p is zero or an integer from 1 to 10; and 
 R 4  is —P(O)(OH) 2 ; or an aryl radical or a heteroaryl radical having up to 14 carbon atoms; or branched-chain alkyl or alkenyl or cycloalkyl each having up to 10 carbon atoms, it being possible for the aryl, heteroaryl, branched alkyl, branched alkenyl or cycloalkyl radicals to be unsubstituted or substituted by one or more of the substituents given in the definition of R 1 ; and X −  is a charge-balancing ion. 
 
   
   
       10 . Use of a compound according to  claim 1  in the manufacture of an electrode or an electrochromic device. 
   
   
       11 . An electrode or an electrochromic device comprising a compound according to  claim 6 . 
   
   
       12 . Use of a compound according to  claim 6  in the manufacture of an electrode or an electrochromic device.