Substituted benzazoloporphyrazines for polymerization and surface attachment and articles formed therefrom

Abstract

The present invention provides an article of manufacture formed from a substrate and a benzazoloporphyrazine bound to the substrate. The article may take a variety of different forms and may be for example an electrochromic display, a molecular capacitor, a battery, a solar cell, or a molecular memory device. Methods of making such articles, along with compounds, methods and intermediates useful for making such benzazoloporphyrazines, are also described.

1 - 24 . (canceled) 
     
     
         25 . A benzazoloporphyrazine compound having at least one independently selected substituent R at a 2 position of an azolo group thereof, wherein R is a surface attachment group or cross coupling group, and subject to the proviso that R is not H or (CH 2 ) n CH 3  where n is 0-7. 
     
     
         26 . A benzazoloporphyrazine according to  claim 25 , wherein said benzazoloporphyrazine is selected from the group consisting of benzimidazoporphyrazines, benzoxazoporphyrazines, benzthiazoporphyrazines, and benzselenazoporphyrazines. 
     
     
         27 . A compound of  claim 25 , wherein said compound is a trans-bis(2-R-benzazolo)porphyrazine having a pair of substituents R at each 2 position of each of the pair of oppositely facing azolo groups thereof. 
     
     
         28 . A benzazoloporphyrazine according to  claim 27 , wherein said benzazoloporphyrazine is selected from the group consisting of benzimidazoporphyrazines, benzoxazoporphyrazines, benzthiazoporphyrazines, and benzselenazoporphyrazines. 
     
     
         29 . The compound of  claim 25 , wherein said compound is a 2-R-benzazoloporphyrazine compound having a single substituent R at the 2 position of the azolo group thereof. 
     
     
         30 . A benzazoloporphyrazine according to  claim 29 , wherein said benzazoloporphyrazine is selected from the group consisting of benzimidazoporphyrazines, benzoxazoporphyrazines, benzthiazoporphyrazines, and benzselenazoporphyrazines. 
     
     
         31 . The compound of  claim 25 , wherein said compound is a tetrakis(2-R-benzazolo)porphyrazine compound having a substituent R at each 2 position of each of the four azolo groups thereof. 
     
     
         32 . A benzazoloporphyrazine according to  claim 31 , wherein said benzazoloporphyrazine is selected from the group consisting of benzimidazoporphyrazines, benzoxazoporphyrazines, benzthiazoporphyrazines, and benzselenazoporphyrazines. 
     
     
         33 . A benzazoloporphyrazine according to  claim 25 , wherein said benzazoloporphyrazine is selected from the group consisting of:
 2-R-5,6-benzimidazoporphyrazines;   trans-bis(2-R-5,6-benzimidazo)porphyrazines;   tribenzo(2-R-5,6-benzimidazo)porphyrazines;   trans-dibenzo-bis(2-R-5,6-benzimidazo)porphyrazines;   tetrakis(2-R-5,6-benzimidazo)porphyrazines;   2-R-5,6-benzoxazoporphyrazines;   trans-bis(2-R-5,6-benzoxazo)porphyrazines;   tribenzo(2-R-5,6-benzoxazo)porphyrazines;   trans-dibenzo-bis(2-R-5,6-benzoxazo)porphyrazines;   tetrakis(2-R-5,6-benzoxazo)porphyrazines;   2-R-5,6-benzthiazoporphyrazines;   trans-bis(2-R-5,6-benzthiazo)porphyrazines;   tribenzo(2-R-5,6-benzthiazo)porphyrazines;   trans-dibenzo-bis(2-R-5,6-benzthiazo)porphyrazines;   tetrakis(2-R-5,6-benzthiazo)porphyrazines;   2-R-5,6-benzselenazoporphyrazines;   trans-bis(2-R-5,6-benzselenazo)porphyrazines;   tribenzo(2-R-5,6-benzselenazo)porphyrazines;   trans-dibenzo-bis(2-R-5,6-benzselenazo)porphyrazines; and   tetrakis(2-R-5,6-benzselenazo)porphyrazines.   
     
     
         34 . The compound of  claim 25 , wherein R comprises a cross-coupling group selected from the group consisting of halo, alkenyl, alkynyl, and amine cross-coupling groups, each of which is directly coupled to said compound or coupled to said compound by a linker group. 
     
     
         35 . The compound of  claim 25 , wherein R comprises a surface attachment group selected from the group consisting of: iodo, bromo, chloro, cyano, amino, alkenyl, alkynyl, hydroxy, mercapto, selenyl, telluro, S-acetylthio, Se-acetylseleno, and Te-acetyltelluro, each of which is directly coupled to said compound or coupled to said compound by a linker group. 
     
     
         36 - 37 . (canceled) 
     
     
         38 . A polymer comprising from 2 to 50 benzazoloporphyrazines of  claim 25  covalently coupled to one another. 
     
     
         39 . (canceled) 
     
     
         40 . A sandwich coordination compound, wherein at least one member thereof is a benzazoloporphyrazine of  claim 25 . 
     
     
         41 - 42 . (canceled) 
     
     
         43 . A polymer of from 2 to 50 linked sandwich coordination compounds, wherein each of said sandwich coordination compounds comprises a benzazoloporphyrazine of  claim 25  linked to a benzazoloporphyrazine of an adjacent sandwich coordination compound. 
     
     
         44 . (canceled) 
     
     
         45 . A method of making a trans-bis(2-R-benzazolo)porphyrazine having a pair of substituents R at each 2 position of a pair of oppositely facing azolo groups thereof, wherein each R is a surface attachment group or cross-coupling group, said method comprising:
 reacting a compound of Formula III:   
       
         
           
           
               
               
           
         
         wherein:
 X is selected from the group consisting of N, O, S, and Se; 
 R is a surface attachment group or cross-coupling group; and 
 R 1  is absent or when X is N is H, C1-C40 linear or branched, substituted or unsubstituted alkyl; and 
 each R 2  is independently selected from the group consisting of H, alkyl, alkenyl, alkynyl, cycloalkyl, aryl (including phenyl), halo, hydroxy, alkoxy, alkylthio, pyridyl, cyano, thiocyanato, nitro, amino, alkylamino, acyl, sulfoxyl, sulfonyl, amido, and carbamoyl; 
 or an R 2  group is linked to an R 2  group on an additional compound of formula III by a linker group; 
 
       
       with a trihaloisoindolenine to produce said trans-bis(2-R-benzazolo)porphyrazine compound. 
     
     
         46 . The method of  claim 45 , wherein said reacting step is carried out in the presence of an acid acceptor and a hydroquinone compound which can donate hydrogen atoms. 
     
     
         47 . The method of  claim 45 , wherein said trihaloisoindolenine is a compound of Formula IV: 
       
         
           
           
               
               
           
         
       
       wherein X 2 , X 3 , and X 4  are each halo and each R 2  is as given above, or a pair of adjacent R 2  groups form an annulated ring or annulated ring system. 
     
     
         48 . The method of  claim 47 , wherein:
 said trans-bis(2-R-benzazolo)porphyrazine is a compound of Formula IIa or IIb:   
       
         
           
           
               
               
           
         
         wherein M is a metal or a pair of hydrogens; and each of X, R, R 1 , and R 2  are as given above. 
       
     
     
         49 . A method of making a 2-R-benzazoloporphyrazine compound having at least one independently selected substituent R at a 2 position of an azolo group thereof, wherein R is a surface attachment group or cross-coupling group, said method comprising:
 reacting a compound of Formula III:   
       
         
           
           
               
               
           
         
         wherein:
 X is selected from the group consisting of N, O, S, and Se; 
 R is a surface attachment group or cross-coupling group; 
 R 1  is absent or when X is N is H, C1-C40 linear or branched, substituted or unsubstituted alkyl, and 
 each R 2  is independently selected from the group consisting of H, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, halo, hydroxy, alkoxy, alkylthio, pyridyl, cyano, thiocyanato, nitro, amino, alkylamino, acyl, sulfoxyl, sulfonyl, amido, and carbamoyl; 
 or an R 2  group is linked to an R 2  group on an additional compound of formula III by a linker group; 
 
         with a substituted or unsubstituted boron-subpporphyrazine in an organic solvent at an elevated temperature to produce said 2-R benzazoloporphyrazine compound. 
       
     
     
         50 . The method of  claim 49 , wherein said 2-benzazoloporphyrazine is a compound of Formula V: 
       
         
           
           
               
               
           
         
         wherein M is a metal or pair of hydrogens, and each of X, R, R 1  and R 2  is as given above. 
       
     
     
         51 . A method of making a 2-R-benzazoloporphyrazine compound, wherein R is a surface attachment group or cross-coupling group, said method comprising:
 reacting a compound of Formula VI:   
       
         
           
           
               
               
           
         
         wherein:
 X is selected from the group consisting of N, O, S, and Se; 
 R is a surface attachment group or cross-coupling group; 
 R 1  is absent or when X is N is H, C1-C40 linear or branched, substituted or unsubstituted alkyl, and 
 each R 2  is independently selected from the group consisting of H, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, halo, hydroxy, alkoxy, alkylthio, pyridyl, cyano, thiocyanato, nitro, amino, alkylamino, acyl, sulfoxyl, sulfonyl, amido, and carbamoyl; 
 or an R 2  group is linked to an R 2  group on an additional compound of formula VI by a linker group; 
 
         with a compound of Formula VII: 
       
       
         
           
           
               
               
           
         
         where R 2  is as given above, or an adjacent pair of R 2  groups on the same ring form a fused or annulated ring or ring system; 
         in an alcohol in the presence of an alkyl amine or metal base, and optionally in the presence of a metal halide, to produce said 2-R-benzazoloporphyrazine compound. 
       
     
     
         52 . The method of  claim 51 , wherein said 2-R benzazoloporphyrazine is a compound of Formula V: 
       
         
           
           
               
               
           
         
         wherein M is a metal or a pair of hydrogens; and each of X, R, R 1  and R 2  is as given above. 
       
     
     
         53 . A method of making a tetrakis (2-R-benzazolo)porphyrazine compound having four substituents R at the 2 position of each azolo group thereof, wherein R is a surface attachment group or cross-coupling group, said method comprising:
 tetramerizing a compound of Formula III:   
       
         
           
           
               
               
           
         
         wherein:
 X is selected from the group consisting of N, O, S, and Se; 
 R is a surface attachment group or cross-coupling group; 
 R 1  is absent or when X is N is H, C 1 -C 40  linear or branched, substituted or unsubstituted alkyl, and 
 each R 2  is independently selected from the group consisting of H, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, halo, hydroxy, alkoxy, alkylthio, pyridyl, cyano, thiocyanato, nitro, amino, alkylamino, acyl, sulfoxyl, sulfonyl, amido, and carbamoyl; 
 or an R 2  group is linked to an R 2  group on an additional compound of formula III by a linker group; 
 
         in a polar protic solvent at an elevated temperature to produce said tetrakis(2-R-benzazolo)porphyrazine compound. 
       
     
     
         54 . The method of  claim 53 , wherein said tetrakis(2-R-benzazolo)porphyrazine is a compound of Formula VIIIa-d: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         wherein M is a metal or a pair of hydrogens and each of X, R, R 1  and R 2  is as given above. 
       
     
     
         55 . A method of making a tetrakis(2-R benzazolo)porphyrazine compound having four substituents R at the 2 position of each azolo group thereof, wherein R is a surface attachment group or cross-coupling group, said method comprising:
 reacting a compound of Formula VI:   
       
         
           
           
               
               
           
         
         wherein:
 X is selected from the group consisting of N, O, S, and Se; 
 R is a surface attachment group or cross-coupling group; 
 R 1  is absent or when X is N is H, C1-C40 linear or branched, substituted or unsubstituted alkyl, and 
 each R 2  is independently selected from the group consisting of H, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, halo, hydroxy, alkoxy, alkylthio, pyridyl, cyano, thiocyanato, nitro, amino, alkylamino, acyl, sulfoxyl, sulfonyl, amido, and carbamoyl; 
 or an R 2  group is linked to an R 2  group on an additional compound of formula VI by a linker group; 
 
         in an alcohol in the presence of an alkyl amine or metal base, and optionally in the presence of a metal halide, to produce said compound. 
       
     
     
         56 . The method of  claim 55 , wherein said tetrakis(2-R benzazolo)porphyrazine is a compound of Formula VIIIa-d: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         wherein M is a metal or a pair of hydrogens and each of X, R, R 1  and R 2  is as given above. 
       
     
     
         57 . A method of making a compound of Formula III: 
       
         
           
           
               
               
           
         
         wherein:
 X is selected from the group consisting of N, O, S, and Se; 
 R is a surface attachment group or cross-coupling group; 
 R 1  is absent or when X is N is H, C1-C40 linear or branched, substituted or unsubstituted alkyl, and 
 each R 2  is independently selected from the group consisting of H, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, halo, hydroxy, alkoxy, alkylthio, pyridyl, cyano, thiocyanato, nitro, amino, alkylamino, acyl, sulfoxyl, sulfonyl, amido, and carbamoyl; 
 
         said method comprising reacting a compound of Formula VI 
       
       
         
           
           
               
               
           
         
         wherein each of X, R, R 1  and R 2  is as given above in either (a) a polar protic solvent with an alkoxide base and ammonia gas at an elevated temperature, or (b) a polar aprotic solvent containing NaNH 2 , to produce said compound of Formula III. 
       
     
     
         58 . A method of making a compound of Formula VI: 
       
         
           
           
               
               
           
         
         wherein:
 X is N, O, S or Se; 
 R is a surface attachment group or cross-coupling group; 
 R 1  is H, C1-C40 linear or branched, substituted or unsubstituted alkyl, and 
 each R 2  is independently selected from the group consisting of H, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, halo, hydroxy, alkoxy, alkylthio, pyridyl, cyano, thiocyanato, nitro, amino, alkylamino, acyl, sulfoxyl, sulfonyl, amido, and carbamoyl; 
 
         said method comprising reacting a compound of Formula IX: 
       
       
         
           
           
               
               
           
         
         
           where X′ is NH 2 , SH, OH, or SeH with an aldehyde of the formula RCHO, wherein R is as given above in a polar aprotic solvent in the presence of an oxidant to produce a reaction product; and then 
           optionally reacting said reaction product with a compound of the formula R 1 X 1 , where X 1  is halo, tosyl, or triflate, to produce said compound of Formula VI. 
         
       
     
     
         59 . A method of making a compound of the Formula IX: 
       
         
           
           
               
               
           
         
         wherein each R 2  is independently selected from the group consisting of H, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, halo, hydroxy, alkoxy, alkylthio, pyridyl, cyano, thiocyanato, nitro, amino, alkylamino, acyl, sulfoxyl, sulfonyl, amido, and carbamoyl; 
         said method comprising reacting a compound of Formula X 
       
       
         
           
           
               
               
           
         
       
       in a polar aprotic solvent with a cyanation reagent to produce said compound of Formula IX.