Substituted benzazoloporphyrazines for polymerization and surface attachment and articles formed therefrom

1. An article of manufacture, comprising:

a substrate; and

a benzazoloporphyrazine bound to said substrate, with said benzazoloporphyrazine bound to said substrate by a bond through a surface attachment group, wherein the surface attachment group has a bond directly or through a linker to the 2 position of an azolo group of said benzazoloporphyrazine.

2. The article of manufacture of claim 1 , said substrate comprising a material selected from the group consisting of conductors, semiconductors, insulators, and composites thereof.

3. The article of manufacture of claim 1 , said substrate comprising a material selected from the group consisting of metals, metal oxides, organic polymers, and composites thereof.

4. The article of manufacture of claim 1 , wherein said bond to said surface attachment group is a covalent bond.

5. The article of manufacture of claim 1 , wherein said article is an electrochromic display.

6. The article of manufacture of claim 1 , wherein said article is a molecular capacitor.

7. The article of manufacture of claim 1 , wherein said article is a battery.

8. The article of manufacture of claim 1 , wherein said article is a solar cell.

9. The article of manufacture of claim 1 , wherein said article is a molecular memory device.

10. The article of manufacture of claim 1 , wherein said benzazoloporphyrazine is a member of a sandwich coordination compound, said coordination compound selected from the group consisting of double-decker sandwich coordination compounds and triple-decker sandwich coordination compounds.

11. The article of manufacture of claim 10 , each of said sandwich coordination compounds selected from the group consisting of heteroleptic sandwich coordination compounds and homoleptic sandwich coordination compounds.

12. The article of manufacture of claim 1 , wherein said benzazoloporphyrazine is a member of a polymer of at least two linked benzazoloporphyrazines, with each of said benzazoloporphyrazines linked to an adjacent benzazoloporphyrazine by a bond through a linker having a bond to the 2 position of an azolo group thereof.

13. The article of manufacture of claim 1 , wherein said benzazoloporphyrazine is selected from the group consisting of benzimidazoporphyrazines, benzoxazoporphyrazines, benzthiazoporphyrazines, and benzselenazoporphyrazines.

14. The article of manufacture of claim 1 , wherein said benzazoloporphyrazine is selected from the group consisting of trans-bis-(2-R-benzazolo)porphyrazines, 2-R-benzazoloporphyrazines, and tetrakis (2-R-benzazolo)porphyrazines wherein R is an independently selected substituent.

15. The article of claim 1 , said benzazoloporphyrazine compound having at least one independently selected substituent R at a 2 position of an azolo group thereof, wherein R is the 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.

16. The article of claim 15 , 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.

17. The article of claim 15 , 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.

18. The article of claim 15 , wherein R comprises the 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.

19. The article of claim 15 , wherein said benzazoloporphyrazine is selected from the group consisting of:

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.

20. An article of manufacture, comprising:

a substrate; and

a polymer bound to said substrate, said polymer comprising a plurality of covalently joined monomeric units, each of said monomeric units comprising an independently selected sandwich coordination compound;

with each of said monomeric units containing at least one benzazoloporphyrazine;

and with each of said benzazoloporphyrazines covalently joined to a benzazoloporphyrazine of an adjacent monomeric unit by a bond to a group, wherein the group has a bond directly or through a linker to the 2 position of the azolo groups of each benzazoloporphyrazine.

21. The article of manufacture of claim 20 , said substrate comprising a material selected from the group consisting of conductors, semiconductors, insulators, and composites thereof.

22. The article of manufacture of claim 20 , said substrate comprising a material selected from the group consisting of metals, metal oxides, organic polymers, and composites thereof.

23. The article of manufacture of claim 20 , wherein said article is an electrochromic display.

24. The article of manufacture of claim 20 , wherein said article is a molecular capacitor.

25. The article of manufacture of claim 20 , wherein said article is a battery.

26. The article of manufacture of claim 20 , wherein said article is a molecular memory device.

27. The article of manufacture of claim 20 , wherein said benzazoloporphyrazine is selected from the group consisting of benzimidazoporphyrazines, benzoxazoporphyrazines, benzthiazoporphyrazines, and benzselenazoporphyrazines.

28. The article of manufacture of claim 20 , wherein said benzazoloporphyrazine is selected from the group consisting of trans-bis(2-R-benzazolo)porphyrazines, 2-R-benzazoloporphyrazines, and tetrakis(2-R-benzazolo)porphyrazines wherein R is an independently selected substituent.

29. The article of claim 20 , said 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.

30. The article of claim 29 , 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.

31. The article of claim 29 , 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.

32. The article of claim 29 , 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.

33. The article of claim 29 , wherein said benzazoloporphyrazine is selected from the group consisting of:

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.