Redox chromophore compounds and electrodes of metal containing substituted bipyridines

• US 4,611,890 A
• Filed: 01/24/1984
• Issued: 09/16/1986
• Est. Priority Date: 01/24/1984
• Status: Expired due to Fees

• Current Assignee: Elliott C. Michael
• Original Assignee: Research Corporation
• Inventors: Redepenning, Jody G., Elliott, Cecil M.
• Primary Examiner(s): Terapane, John F.
• Assistant Examiner(s): Kilby, Catherine S.
• Application Number:
  US06/573,886
• Time in Patent Office: 966 Days
• Field of Search: 252/600, 252/408.1, 350/357, 526/265, 427/108, 445/58
• US Class Current: 359/265
• CPC Class Codes: B41M 5/20 using electric current B41M5/24 takes precedence ; processes in which the current is transformed into a heat pattern for obtaining transfer to a receptor sheet B41M5/382; electro-coagulable or electro-adhesive printing or recording B41C1/105
• CPC Class Codes: C08F 20/36 containing oxygen in addition to the carboxy oxygen , e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
• CPC Class Codes: C08F 20/60 containing nitrogen in addition to the carbonamido nitrogen
• CPC Class Codes: G02F 1/1503 caused by oxidation-reduction reactions in organic liquid solutions, e.g. viologen solutions

Abstract

Chromophoric compounds, each having a wide range of distinct color changes in response to changes in the oxidation states thereof, are provided in the form of polymerizable monomers, and polymers thereof, of certain metal containing, and electron group substituted, 2,2'"'"'-bipyridine compounds.

Claims

1. A polymer consisting of at least one compound having the structure ##STR22## wherein Me is chromium or a Group VIII metal, Ligand A is 4,4'"'"' or 5,5'"'"' substituted 2,2'"'"'bipyridyl group of the structure ##STR23## wherein A'"'"' and A" are the same or different in each Ligand A and have the structure ##STR24## wherein R is C₂ to C₁₈ alkyl and R_i is H or CH₃, Y and Y'"'"' are the same or different and are --O-- or ##STR25## and R_iv is a C₁ to C₈ alkyl radical, and Ligand B is an unsubstituted 2,2'"'"'-dipyridyl radical, a 2,2'"'"'-dipyridyl radical substituted with only one or more hydrocarbon radicals, or is a 4,4'"'"' or a 5,5'"'"' substituted 2,2'"'"' bipyridyl group of the structure shown above which is the same or different from that of Ligand A,

X is a compatible anion,

a and b are integers, a is 1, 2, or 3, b is 0, 1 or 2 and a+b=1, 2, or 3, and

n" is an integer which is 1, 2 or 3.

2. A polymer as in claim 1 wherein Me is selected from the group consisting of ruthenium, iron, cobalt and nickel.

3. A polymer as in claim 2 in which Me is ruthenium.

4. A polymer as in claim 2 wherein b is 0.

5. A polymer as in claim 4 in which Ligand A is a 5,5'"'"' substituted-2,2'"'"'-bipyridyl group.

6. A polymer as in claim 5 in which R_i is H.

7. A polymer as in claim 6 in which R is propyl.

8. An electrode coated with a chromophorically useful layer of a polymer of claim 1.

9. An electrode coated with a chromophorically useful layer of a polymer of claim 3.

10. An electrode coated with a chromophorically useful layer of a polymer of claim 7.

11. In an electronic display device comprising at least one solid chromophore on an electrode, the improvement comprising employing as said electrode that of claim 8.

12. In an electronic display device comprising at least one solid chromophore on an electrode, the improvement comprising employing as said electrode that of claim 9.

13. In an electronic display device comprising at least one solid chromophore on an electrode, the improvement comprising employing as said electrode that of claim 10.

14. An electrode as in claim 8 in which said layer is about 1 to 5 microns thick.

15. An electrode as in claim 14 which is tin oxide.

16. A copolymer of at least one compound of Structure I and at least one compound of Structure II wherein said Structure I compound has the structure ##STR26## wherein Me is chromium or a Group VIII metal, Ligand A is a 4,4'"'"' or 5,5'"'"' substituted 2,2'"'"' bipyridyl group of the Structure IA ##STR27## wherein A'"'"' and A" are the same or different in each Ligand A and have the Structure IB ##STR28## wherein R is C₂ to C₁₈ alkyl and R_i is H or CH₃, Y and Y'"'"' are the same or different and are --O-- or ##STR29## and R_ir is a C₁ to C₈ alkyl radical, and Ligand B is an unsubstituted 2,2'"'"'-dipyridyl radical, a 2,2'"'"'-dipyridyl radical substituted with only one or more hydrocarbon radicals, or is a 4,4'"'"' or a 5,5'"'"' substituted 2,2'"'"' bipyridyl group of said Structure IA which is the same as, or different from, that of Ligand A,

X is a compatible anion,

a and b are integers, a is 1, 2, or 3, b is 0, 1 or 2 and a+b=1, 2, or 3, and

n" is an integer which is 1, 2 or 3, and

said Structure II compound has at least one of the Structures IIA and IIB which are the structures ##STR30## wherein y and y'"'"' are integers which may be the same or different and y is 2 to 32 and y'"'"' is 0 to 32.

17. A copolymer as in claim 16 wherein Me is ruthenium.

18. A copolymer as in claim 17 wherein b is 0.

19. A copolymer as in claim 18 wherein Ligand A is a 5,5'"'"' substituted-2,2'"'"'-bipyridyl group.

20. A copolymer as in claim 19 wherein R_i is H.

21. A copolymer as in claim 20 wherein R is propyl.

22. A copolymer as in claim 16 formed from at least one compound of Structure I and at least one compound of Structure IIA.

23. A copolymer as in claim 16 formed from at least one compound of Structure I and at least one compound of Structure IIB.

24. A polymer formed from a monomer charge comprising at least one compound having the Structure III ##STR31## wherein Me is chromium or a Group VIII metal, Ligand A is a 4,4'"'"' or 5,5'"'"' substituted 2,2'"'"'bipyridyl group of the Structure IIIA ##STR32## wherein A'"'"' is A" are the same or different in each Ligand A and have the Structure IIIB ##STR33## wherein R is C₂ to C₁₈ alkyl and R_i is H or CH₃, Y and Y'"'"' are the same or different and are --O-- or ##STR34## and R_iv is a C₁ to C₈ alkyl radical, and Ligand B is an unsubstituted 2,2'"'"'-dipyridyl radical, a 2,2'"'"'-dipyridyl radical substituted with only one or more hydrocarbon radicals, or is a 4,4'"'"' or 5,5'"'"' substituted 2,2'"'"' bipyridyl group of said Structure IIIA which is the same as, or different from, that of Ligand A,

X is a compatible anion,

a and b are integers, a is 1, 2, or 3, b is 0, 1 or 2 and a+b=1, 2, or 3, and

n" is an integer which is 1, 2 or 3.

25. A polymer as in claim 24 wherein Me is selected from the group consisting of ruthenium, iron, cobalt and nickel.

26. A polymer as in claim 25 in which Me is ruthenium.

27. A polymer as in claim 26 wherein b is 0.

28. A polymer as in claim 27 in which Ligand A is a 5,5'"'"' substituted 2,2'"'"'-bipyridyl group.

29. A polymer as in claim 28 in which R_i is H.

30. A polymer as in claim 29 in which R is propyl.

31. An electrode coated with a chromophorically useful layer of a polymer of claim 24.

32. An electrode coated with a chromophorically useful layer of a polymer of claim 26.

33. An electrode coated with a chromophorically useful layer of a polymer of claim 30.

34. In an electronic display device comprising at least one solid chromophore on an electrode, the improvement comprising employing as said electrode that of claim 31.

35. In an electronic display device comprising at least one solid chromophore on an electrode, the improvement comprising employing as said electrode that of claim 32.

36. In an electronic display device comprising at least one solid chromophore on an electrode, the improvement comprising employing as said electrode that of claim 33.

37. An electrode as in claim 31 in which said layer is about 1 to 5 microns thick.

38. An electrode as in claim 37 which is tin oxide.