Electrochromic medium capable of producing a pre-selected color

• US 6,020,987 A
• Filed: 04/02/1997
• Issued: 02/01/2000
• Est. Priority Date: 04/02/1997
• Status: Expired due to Term

• Current Assignee: Gentex Corporation
• Original Assignee: Gentex Corporation
• Inventors: Siegrist, Kathy E., Guarr, Thomas F., Byker, Harlan J., Winkle, Derick D., Theiste, David A., Baumann, Kelvin L.
• Primary Examiner(s): Epps, Georgia
• Assistant Examiner(s): BEY, DAWN MARIE
• Application Number:
  US08/832,596
• Time in Patent Office: 1,035 Days
• Field of Search: 359/273
• US Class Current: 359/273
• CPC Class Codes: B32B 17/10036 comprising two outer glass sheets
• CPC Class Codes: B32B 17/10174 Coatings of a metallic or dielectric material on a constituent layer of glass or polymer
• CPC Class Codes: B32B 17/10302 Edge sealing
• CPC Class Codes: B32B 17/10513 Electrochromic layer
• CPC Class Codes: C09K 9/02 Organic tenebrescent materials
• CPC Class Codes: G02F 1/1503 caused by oxidation-reduction reactions in organic liquid solutions, e.g. viologen solutions
• CPC Class Codes: G02F 1/1516 comprising organic material
• CPC Class Codes: G02F 1/1524 Transition metal compounds
• CPC Class Codes: G02F 2001/15145 the electrochromic layer comprises a mixture of anodic and cathodic compounds

Abstract

An improved electrochromic device, the device incorporating an electrochromic medium that comprises at least three electroactive materials having absorption spectra that add together such that the color of the electrochromic medium can be pre-selected by individually choosing the concentrations of the at least three electroactive materials. The electrochromic medium generally maintains the pre-selected perceived color throughout its normal range of voltages when used in an electrochromic device. The at least three electroactive materials include at least one electrochemically reducible material (cathodic material), at least one electrochemically oxidizable material (anodic material) and at least one additional electroactive material which may be either an anodic or cathodic material. Thus, there are always three electroactive materials present in the medium, with at least two either being anodic or cathodic materials. The pre-selected color may be chosen from a wide variety of colors and may be, for example, red, orange, yellow, green, blue, purple. For electrochromic mirrors for motor vehicles, a presently preferred color is gray.

Claims

1. An electrochromic device, comprising:

front and rear spaced elements each having front and rear surfaces;

a layer of transparent conductive material disposed on said rear surface of said front element and said front surface of said rear element, and a perimeter sealing member bonding together said front and rear spaced elements in a spaced-apart relationship to define a chamber therebetween

where said chamber contains an electrochromic medium, said electrochromic medium comprising at least three electroactive materials, at least two of which are electrochromic, where said medium generally maintains a pre-selected perceived color throughout the normal voltage range of said electrochromic device.

2. The electrochromic device of claim 1, wherein the concentrations of said at least three electroactive materials are chosen to produce a pre-selected perceived color.

3. The electrochromic device of claim 1, wherein said electrochromic device does not exhibit staging.

4. The electrochromic device of claim 1, wherein said at least two electrochromic materials include at least one electrochemically reducible material and at least one electrochemically oxidizable material.

5. The electrochromic device of claim 1, wherein said at least two electrochromic materials are both electrochemically reducible materials or both electrochemically oxidizable materials.

6. The electrochromic device of claim 1, wherein one of said electrochromic materials is selected from the group consisting of:

surface confined and electrodeposition.

7. The electrochromic device of claim 1, wherein all of said electroactive materials are solution-phase.

8. The electrochromic device of claim 7, wherein the redox potentials of all of said electroactive materials that are anodic are within about 200 mV of one another, and wherein the redox potentials of all of said electroactive materials that are cathodic are within about 200 mV of one another.

9. The electrochromic device of claim 8, wherein the redox potentials of all of said electroactive materials that are anodic are within 60 mV of one another, and wherein the redox potentials of all of said electro active materials that are cathodic are within 60 mV of one another.

10. The electrochromic device of claim 9, wherein the redox potentials of all of said electroactive materials that are anodic are within 40 mV of one another, and wherein the redox potentials of all of said electroactive materials that are cathodic are within 40 mV of one another.

11. The electrochromic device of claim 10, wherein said electrochromic device does not exhibit staging.

12. The electrochromic device of claim 1, wherein the redox potentials of all of said electroactive materials that are anodic are within about 200 mV of one another, and wherein the redox potentials of all of said electroactive materials that are cathodic are within about 200 mV of one another.

13. The electrochromic device of claim 12, wherein the redox potentials of all of said electroactive materials that are anodic are within 60 mV of one another, and wherein the redox potentials of all of said electroactive materials that are cathodic are within 60 mV of one another.

14. The electrochromic device of claim 13, wherein the redox potentials of all of said electroactive materials that are anodic are within 40 mV of one another, and wherein the redox potentials of all of said electroactive materials that are cathodic are within 40 mV of one another.

15. The electrochromic device of claim 1, wherein said at least three electroactive species include at least one cathodic material selected from the group consisting of salts of:

1,1'"'"'-diphenyl-4,4'"'"'-dipyridinium;

1,1'"'"'-bis(2,6-dimethylphenyl)-4,4'"'"'-dipyridinium;

1,1'"'"'-bis(3,5-dimethylphenyl)-4,4'"'"'-dipyridinium;

1-phenyl-1'"'"'-(4-dodecylphenyl)-4,4'"'"'-dipyridinium;

1,1'"'"'-bis(2,4,6-trimethylphenyl)-4,4'"'"'-dipyridinium;

1-(3,5-dimethoxyphenyl)-1-methyl-4,4'"'"'-dipyridinium;

1-methyl-1'"'"'-phenyl-4,4'"'"'-dipyridinium;

1-methyl-1'"'"'-(2-methylphenyl)-4,4'"'"'-dipyridinium;

1-(4-methoxyphenyl)-1'"'"'-methyl-4,4'"'"'-dipyridinium;

1-methyl-1'"'"'-(2,4,6-trimethylphenyl)-4,4'"'"'-dipyridinium;

1,2,6-trimethyl-1'"'"'-phenyl-4,4'"'"'-dipyridinium;

1,1'"'"'-dimethyl-2,6-diphenyl-4,4'"'"'-dipyridinium;

1,1'"'"'-bis(3-phenyl(n-propyl))-4,4'"'"'-dipyridinium;

1,1'"'"'-dimethyl-4,4'"'"'-dipyridinium;

1,1'"'"'-dimethyl-2-(3-phenyl(n-propyl))-4,4'"'"'-dipyridinium;

1,1'"'"'-dimethyl-4,4'"'"'-(1,3,5-triazine-2,4-diyl)dipyridinium;

1,1'"'"'-dibenzyl-2,2'"'"',6,6'"'"'-tetramethyl-4,4'"'"'-dipyridinium;

1,1'"'"'-ethylene4,4'"'"'-dimethyl-2,2'"'"'-dipyridinium; and

1,1'"'"'-dimethyl-2,2'"'"'-bis(3-phenyl(n-propyl))-4,4'"'"'-dipyridinium, and wherein said at least three electroactive species include at least one anodic material selected from the group consisting of;

N,N,N'"'"',N'"'"'-tetramethyl-p-phenylenediamine;

2,5,10-trimethyl-3-phenyl-5,10-dihydrophenazine;

5-ethyl-10-methyl5,10-dihydrophenazine;

5,10-dimethyl-5,10-dihydrobenzo(A)phenazine;

2,7-diphenoxy5,10-dimethyl-5,10-dihydrophenazine;

2-phenoxy-5,10-dimethyl-5,10-dihydrophenazine;

2,7-bis(o-tolyl)-5,10-dimethyl-5,10-dihydrophenazine;

2,3-dimethyl-7-trifluoromethyl-5,10-diethyl-5,10-dihydrophenazine;

5,10-dimethyl-5,10-dihydrophenazine;

2,3-diphenyl-5,10-dimethyl-5,10-dihydrophenazine;

2,7-diphenyl-5,10-dimethyl-5,10-dihydrophenazine;

2-vinyl-5,10-dimethyl-5,10-dihydrophenazine;

2-phenyl-5,10-dimethyl-5,10-dihydrophenazine;

5,10-diisopropyl-5,10-dihydrophenazine;

5,10-dimethyl-5,10-dihydrodibenzo(A,C)phenazine 1,5,10-trimethyl-2-phenyl-5,10-dihydrophenazine;

2,3,5,10-tetramethyl-7-trifluoromethyl-5,10-dihydrophenazine; and

2,3,5,10-tetramethyl-5,10-dihydrobenzo(B)phenazine.

16. The electrochromic device of claim 1, wherein said at least three electroactive species include approximately 17 millimolar of 5,10-dimethyl-5,10-dihydrophenazine, approximately 8.5 millimolar of 2-phenyl-5,10-dimethyl-5,10-dihydrophenazine, approximately 4.3 millimolar of 2,3-diphenyl-5,10-dimethyl-5,10-dihydrophenazine, approximately 17 millimolar of 1,1'"'"'-dibenzyl-2,2,6,6'"'"'-tetramethyl4,4'"'"'-dipyridinium bis(tetrafluoroborate), and approximately 17 millimolar of 1,1'"'"'-ethylene-4,4'"'"'-dimethyl-2,2'"'"'-dipyridinium bis(hexafluorophosphate).

17. The electrochromic device of claim 1, wherein said at least three electroactive species include approximately 17 millimolar of 5,10-dimethyl-5,10-dihydrophenazine, approximately 8.5 millimolar of 2-phenyl-5,10-dimethyl-5,10-dihydrophenazine, approximately 4.3 millimolar of 2,3-diphenyl-5,10-dimethyl-5,10-dihydrophenazine, approximately 19 millimolar of 1,1'"'"'-dibenzyl-2,2'"'"',6,6'"'"'-tetramethyl4,4'"'"'-dipyridinium bis(tetrafluoroborate), and approximately 15 millimolar of 1,1'"'"'-ethylene-4,4'"'"'-dimethyl-2,2'"'"'-dipyridinium bis(hexafluorophosphate).

18. The electrochromic device of claim 1, wherein said pre-selected perceived color is a member of the group consisting of red, yellow, green, blue, purple, and gray.

19. The electrochromic device of claim 18, wherein said pre-selected color is gray.

20. The electrochromic device of claim 19, wherein at least one of said electroactive materials includes a 5,10-dialkyl-5,10-dihydrophenazine where at least one of said 2, 3, 7 and 8 positions contain a member of the group consisting of:

phenyl;

substituted phenyl;

vinyl; and

phenoxy.

21. The electrochromic device of claim 19, wherein at least one of said electroactive materials includes a cathodic electrochromic material selected from the group consisting of salts of:

1,1'"'"'-diphenyl-4,4'"'"'-dipyridinium;

1,1'"'"'-bis(2,6-dimethylphenyl)-4,4'"'"'-dipyridinium;

1,1'"'"'-bis(3,5-dimethylphenyl)-4,4'"'"'-dipyridinium;

1-phenyl-1'"'"'-(4-dodecylphenyl)-4,4'"'"'-dipyridinium;

1,1'"'"'-bis(2,4,6-trimethylphenyl)-4,4'"'"'-dipyridinium;

1-(3,5-dimethoxyphenyl)-1'"'"'-methyl-4,4'"'"'-dipyridinium;

1-methyl-1'"'"'-phenyl-4,4'"'"'-dipyridinium;

1-methyl-1'"'"'-(2-methylphenyl)-4,4'"'"'-dipyridinium;

1-(4-methoxyphenyl)-1'"'"'-methyl-4,4'"'"'-dipyridinium;

1-methyl-1'"'"'-(2,4,6-trimethylphenyl)-4,4'"'"'-dipyridinium;

1,2,6-trimethyl-1'"'"'-phenyl-4,4'"'"'-dipyridinium;

1,1'"'"'-dimethyl-2,6-diphenyl4,4'"'"'-dipyridinium;

1,1'"'"'-bis(3-phenyl(n-propyl))-4,4'"'"'-dipyridinium;

1,1'"'"'-dimethyl-4,4'"'"'-dipyridinium;

1,1'"'"'-dimethyl-2-(3-phenyl(n-propyl))-4,4'"'"'-dipyridinium;

1,1'"'"'-dimethyl-4,4'"'"'-(1,3,5-triazine-2,4-diyl)dipyridinium;

1,1'"'"'-dibenzyl-2,2'"'"',6,6'"'"'-tetramethyl-4,4'"'"'-dipyridinium;

1,1'"'"'-ethylene-4,4'"'"'-dimethyl-2,2'"'"'-dipyridinium; and

1,1'"'"'-dimethyl-2,2'"'"'-bis(3-phenyl(n-propyl))-4,4'"'"'-dipyridinium.

22. The electrochromic device of claim 19, wherein said device maintains a transmittance spectrum resulting in color coordinates (A/2 degree) such that C* is between zero and about 22.

23. The electrochromic device of claim 22, wherein said device maintains transmittance spectrum resulting in color coordinates (A/2 degree) such that a* is between zero and about -18.

24. The electrochromic device of any of claims 1-23, wherein said electrochromic device is a member of the group consisting of:

an electrochromic window, a display device, and a motor vehicle sunroof.

73. The electrochromic device according to claims 1 and 25, wherein said electrochromic medium is gray and wherein said transparent conductor on said rear surface of front element is color suppressed.

25. An electrochromic device, comprising:

front and rear spaced elements each having front and rear surfaces;

a layer of transparent conductive material disposed on said rear surface of said front element and said front surface of said rear element, and a perimeter sealing member bonding together said front and rear spaced elements in a spaced-apart relationship to define a chamber therebetween where said chamber contains an electrochromic medium, said electrochromic medium comprising at least three electroactive materials, at least two of which are electrochromic, where the redox potentials of all of said electroactive materials that are anodic are within about 200 mV of one another, and wherein the redox potentials of all of said electroactive materials that are cathodic are within about 200 mV of one another.

26. The electrochromic device of claim 25, wherein the redox potentials of all of said electroactive materials that are anodic are within 60 mV of one another, and wherein the redox potentials of all of said electroactive materials that are cathodic are within 60 mV of one another.

27. The electrochromic device of claim 26, wherein the redox potentials of all of said electroactive materials that are anodic are within 40 mV of one another, and wherein the redox potentials of all of said electroactive materials that are cathodic are within 40 mV of one another.

28. The electrochromic device of claim 25, wherein said at least three electroactive species include at least one cathodic material selected from the group consisting of salts of:

1,1'"'"'-diphenyl-4,4'"'"'-dipyridinium;

1,1'"'"'-bis(2,6-dimethylphenyl)-4,4'"'"'-dipyridinium;

1,1'"'"'-bis(3,5-dimethylphenyl)-4,4'"'"'-dipyridinium;

1-phenyl-1'"'"'-(4-dodecylphenyl)-4,4'"'"'-dipyridinium;

1,1'"'"'-bis(2,4,6-trimethylphenyl)-4,4'"'"'-dipyridinium;

1-(3,5-dimethoxyphenyl)-1'"'"'-methyl-4,4'"'"'-dipyridinium;

1-methyl-1'"'"'-phenyl-4,4'"'"'-dipyridinium;

1-methyl-1'"'"'-(2-methylphenyl)-4,4'"'"'-dipyridinium;

1-(4-methoxyphenyl)-1'"'"'-methyl-4,4'"'"'-dipyridinium;

1-methyl-1'"'"'-(2,4,6-trimethylphenyl)-4,4'"'"'-dipyridinium;

1,2,6-trimethyl-1'"'"'-phenyl-4,4'"'"'-dipyridinium;

1,1'"'"'-dimethyl-2,6-diphenyl-4,4'"'"'-dipyridinium;

1,1'"'"'-bis(3-phenyl(n-propyl))-4,4'"'"'-dipyridinium;

1,1'"'"'-dimethyl-4,4'"'"'-dipyridinium;

1,1'"'"'-dimethyl-2-(3-phenyl(n-propyl))-4,4'"'"'-dipyridinium;

1,1'"'"'-dimethyl-4,4'"'"'-(1,3,5-triazine-2,4-diyl)dipyridinium;

1,1'"'"'-dibenzyl-2,2'"'"',6,6'"'"'-tetramethyl-4,4'"'"'-dipyridinium;

1,1'"'"'-ethylene-4,4'"'"'-dimethyl-2,2'"'"'-dipyridinium; and

1,1'"'"'-dimethyl-2,2'"'"'-bis(3-phenyl(n-propyl))-4,4'"'"'-dipyridinium, and wherein said at least three electroactive species include at least one anodic material selected from the group consisting of;

N,N,N'"'"',N'"'"'-tetramethyl-p-phenylenediamine;

2,5,10-trimethyl-3-phenyl-5,10-dihydrophenazine;

5-ethyl-10-methyl-5,10-dihydrophenazine;

5,10-dimethyl-5,10-dihydrobenzo(A)phenazine;

2,7-diphenoxy-5,10-dimethyl-5,10-dihydrophenazine;

2-phenoxy-5,10-dimethyl-5,10-dihydrophenazine;

2,7-bis(o-tolyl)-5,10-dimethyl-5,10-dihydrophenazine;

2,3-dimethyl-7-trifluoromethyl-5,10-diethyl-5,10-dihydrophenazine;

5,10-dimethyl-5,10-dihydrophenazine;

2,3-diphenyl-5,10-dimethyl-5,10-dihydrophenazine;

2,7-diphenyl-5,10-dimethyl-5,10-dihydrophenazine;

2-vinyl-5,10-dimethyl-5,10-dihydrophenazine;

2-phenyl-5,10-dimethyl-5,10-dihydrophenazine;

5,10-diisopropyl-5,10-dihydrophenazine;

5,10-dimethyl-5,10-dihydrodibenzo(A,C)phenazine 1,5,10-trimethyl-2-phenyl-5,10-dihydrophenazine;

2,3,5,10-tetramethyl-7-trifluoromethyl-5,10-dihydrophenazine; and

2,3,5,10-tetramethyl-5,10-dihydrobenzo(B)phenazine.

29. The electrochromic device of claim 25, wherein said at least three electroactive species include approximately 17 millimolar of 5,10-dimethyl-5,10-dihydrophenazine, approximately 8.5 millimolar of 2-phenyl-5,10-dimethyl-5,10-dihydrophenazine, approximately 4.3 millimolar of 2,3-diphenyl-5,10-dimethyl-5,10-dihydrophenazine, approximately 17 millimolar of 1,1'"'"'-dibenzyl-2,2'"'"',6,6'"'"'-tetramethyl-4,4'"'"'-dipyridinium bis(tetrafluoroborate), and approximately 17 millimolar of 1,1'"'"'-ethylene-4,4'"'"'-dimethyl-2,2'"'"'-dipyridimium bis(hexafluorophosphate).

30. The electrochromic device of claim 25, wherein said at least three electroactive species include approximately 17 millimolar of 5,10-dimethyl-5,10-dihydrophenazine, approximately 8.5 millimolar of 2-phenyl-5,10-dimethyl-5,10-dihydrophenazine, approximately 4.3 millimolar of 2,3-diphenyl-5,10-dimethyl-5,10-dihydrophenazine, approximately 19 millimolar of 1,1'"'"'-dibenzyl-2,2'"'"',6,6'"'"'-tetramethyl-4,4'"'"'-dipyridinium bis(tetrafluoroborate), and approximately 15 millimolar of 1,1'"'"'-ethylene-4,4'"'"'-dimethyl-2,2'"'"'-dipyridinium bis(hexafluorophosphate).

31. The electrochromic device of claim 25, wherein said pre-selected color is a member of the group consisting of red, yellow, green, blue, purple, and gray.

32. The electrochromic device of claim 31, wherein said pre-selected color is gray.

33. The electrochromic device of claim 32, wherein at least one of said electroactive materials includes a 5,10-dialkyl-5,10-dihydrophenazine where at least one of said 2, 3, 7 and 8 positions contain a member of the group consisting of:

phenyl;

substituted phenyl;

vinyl; and

phenoxy.

34. The electrochromic device of claim 33, wherein at least one of said electroactive materials includes a cathodic electrochromic material selected from the group consisting of salts of:

1,1'"'"'-diphenyl-4,4'"'"'-dipyridinium;

1,1'"'"'-bis(2,6-dimethylphenyl)-4,4'"'"'-dipyridinium;

1,1'"'"'-bis(3,5-dimethylphenyl)-4,4'"'"'-dipyridinium;

1-phenyl-1'"'"'-(4-dodecylphenyl)-4,4'"'"'-dipyridinium;

1,1'"'"'-bis(2,4,6-trimethylphenyl)-4,4'"'"'-dipyridinium;

1-(3,5-dimethoxyphenyl)-1'"'"'-methyl-4,4'"'"'-dipyridinium;

1-methyl-1-phenyl4,4'"'"'-dipyridinium;

1-methyl-1'"'"'-(2-methylphenyl)-4,4'"'"'-dipyridinium;

1-(4-methoxyphenyl)-1-methyl-4,4'"'"'-dipyridinium;

1-methyl-1'"'"'-(2,4,6-trimethylphenyl)-4,4'"'"'-dipyridinium;

1,2,6-trimethyl-1'"'"'-phenyl-4,4'"'"'-dipyridinium;

1,1'"'"'-dimethyl-2,6-diphenyl4,4'"'"'-dipyridinium;

1,1'"'"'-bis(3-phenyl(n-propyl))-4,4'"'"'-dipyridinium;

1,1'"'"'-dimethyl-4,4'"'"'-dipyridinium;

1,1'"'"'-dimethyl-2-(3-phenyl(n-propyl))-4,4'"'"'-dipyridinium;

1,1'"'"'-dimethyl-4,4'"'"'-(1,3,5-triazine-2,4-diyl)dipyridinium;

1,1'"'"'-dibenzyl-2,2'"'"',6,6'"'"'-tetramethyl-4,4'"'"'-dipyridinium;

1,1'"'"'-ethylene-4,4'"'"'-dimethyl-2,2'"'"'-dipyridinium; and

1,1'"'"'-dimethyl-2,2'"'"'-bis(3-phenyl(n-propyl))-4,4'"'"'-dipyridinium.

35. The electrochromic device of claim 32, wherein said device maintains a transmittance spectrum resulting in color coordinates (A/2 degree) such that C* is between zero and about 22.

36. The electrochromic device of claim 35, wherein said device maintains transmittance spectrum resulting in color coordinates (A/2 degree) such that a* is between zero and about -18.

37. The electrochromic device of claim 25, wherein said electrochromic device is a member of the group consisting of:

an electrochromic window, a display device, and a motor vehicle sunroof.

38. An electrochromic variable reflectance mirror for automotive vehicles, comprising:

front and rear spaced elements each having front and rear surfaces;

a layer of transparent conductive material disposed on said rear surface of said front element;

a reflector disposed on one side of said rear element provided that, if said reflector is on said rear surface of said rear element, then said front surface of said rear element contains a layer of a transparent conductive material; and

a perimeter sealing member bonding together said front and rear spaced elements in a spaced-apart relationship to define a chamber therebetween;

where said chamber contains an electrochromic medium, said electrochromic medium comprising at least three electroactive materials, at least two of which are electrochromic, where said medium generally maintains a pre-selected perceived color throughout the normal voltage range of said electrochromic device.

39. The electrochromic mirror of claim 38, wherein the concentrations of said at least three electroactive materials are chosen to produce a pre-selected perceived color.

40. The electrochromic mirror of claim 38, wherein said electrochromic mirror does not exhibit staging.

41. The electrochromic mirror of claim 38, wherein said at least two electrochromic materials include at least one electrochemically reducible material and at least one electrochemically oxidizable material.

42. The electrochromic mirror of claim 41, wherein said electrochromic medium further comprises at least one additional electroactive material selected from the group consisting of anodic electrochromic materials and cathodic electrochromic materials.

43. The electrochromic mirror of claim 38, wherein one of said electrochromic materials is selected from the group consisting of:

surface confined and electrodeposition.

44. The electrochromic mirror of claim 38, wherein all of said electroactive materials are solution-phase.

45. The electrochromic mirror of claim 44, wherein the redox potentials of all of said electroactive materials that are anodic are within about 200 mV of one another, and wherein the redox potentials of all of said electroactive materials that are cathodic are within about 200 mV of one another.

46. The electrochromic mirror of claim 45, wherein the redox potentials of all of said electroactive materials that are anodic are within 60 mV of one another, and wherein the redox potentials of all of said electroactive materials that are cathodic are within 60 mV of one another.

47. The electrochromic mirror of claim 46, wherein the redox potentials of all of said electroactive materials that are anodic are within 40 mV of one another, and wherein the redox potentials of all of said electroactive materials that are cathodic are within 40 mV of one another.

48. The electrochromic mirror of claim 47, wherein said electrochromic mirror does not exhibit staging.

49. The electrochromic mirror of claim 38, wherein the redox potentials of all of said electroactive materials that are anodic are within about 200 mV of one another, and wherein the redox potentials of all of said electroactive materials that are cathodic are within about 200 mV of one another.

50. The electrochromic mirror of claim 49, wherein the redox potentials of all of said electroactive materials that are anodic are within 60 mV of one another, and wherein the redox potentials of all of said electro active materials that are cathodic are within 60 mV of one another.

51. The electrochromic mirror of claim 50, wherein the redox potentials of all of said electroactive materials that are anodic are within 40 mV of one another, and wherein the redox potentials of all of said electroactive materials that are cathodic are within 40 mV of one another.

52. The electrochromic mirror of claim 38, wherein said at least three electroactive species include at least one cathodic material selected from the group consisting of salts of:

1,1'"'"'-diphenyl-4,4'"'"'-dipyridinium;

1,1'"'"'-bis(2,6-dimethylphenyl)-4,4'"'"'-dipyridinium;

1,1'"'"'-bis(3,5-dimethylphenyl)-4,4'"'"'-dipyridinium;

1-phenyl-1'"'"'-(4-dodecylphenyl)-4,4'"'"'-dipyridinium;

1,1'"'"'-bis(2,4,6-trimethylphenyl)-4,4'"'"'-dipyridinium;

1-(3,5-dimethoxyphenyl)-1'"'"'-methyl-4,4'"'"'-dipyridinium;

1-methyl-1'"'"'-phenyl-4,4'"'"'-dipyridinium;

1-methyl-1'"'"'-(2-methylphenyl)-4,4'"'"'-dipyridinium;

1-(4-methoxyphenyl)- 1'"'"'-methyl-4,4'"'"'-dipyridinium;

1-methyl-1'"'"'-(2,4,6-trimethylphenyl)-4,4'"'"'-dipyridinium;

1,2,6-trimethyl-1'"'"'-phenyl-4,4'"'"'-dipyridinium;

1,1'"'"'-dimethyl-2,6-diphenyl-4,4'"'"'-dipyridinium;

1,1'"'"'-bis(3-phenyl(n-propyl))-4,4'"'"'-dipyridinium;

1,1'"'"'-dimethyl-4,4'"'"'-dipyridinium;

1,1'"'"'-dimethyl-2-(3-phenyl(n-propyl))-4,4'"'"'-dipyridinium;

1,1'"'"'-dimethyl-4,4'"'"'-(1,3,5-triazine-2,4-diyl)dipyridinium;

1,1'"'"'-dibenzyl-2,2'"'"',6,6'"'"'-tetramethyl-4,4'"'"'-dipyridinium;

1,1'"'"'-ethylene-4,4'"'"'-dimethyl-2,2'"'"'-dipyridinium; and

1,1'"'"'-dimethyl-2,2'"'"'-bis(3-phenyl(n-propyl))-4,4'"'"'-dipyridinium, and wherein said at least three electroactive species include at least one anodic material selected from the group consisting of;

N,N,N'"'"',N'"'"'-tetramethyl-p-phenylenediamine;

2,5,10-trimethyl-3-phenyl-5,10-dihydrophenazine;

5-ethyl-10-methyl-5,10-dihydrophenazine;

5,10-dimethyl-5,10-dihydrobenzo(A)phenazine;

2,7-diphenoxy-5,10-dimethyl-5,10-dihydrophenazine;

2-phenoxy-5,10-dimethyl-5,10-dihydrophenazine;

2,7-bis(o-tolyl)-5,10-dimethyl-5,10-dihydrophenazine;

2,3-dimethyl-7-trifluoromethyl-5,10-diethyl-5,10-dihydrophenazine;

5,10-dimethyl-5,10-dihydrophenazine;

2,3-diphenyl-5,10-dimethyl-5,10-dihydrophenazine;

2,7-diphenyl-5,10-dimethyl-5,10-dihydrophenazine;

2-vinyl-5,10-dimethyl-5,10-dihydrophenazine;

2-phenyl-5,10-dimethyl-5,10-dihydrophenazine;

5,10-diisopropyl-5,10-dihydrophenazine;

5,10-dimethyl-5,10-dihydrodibenzo(A,C)phenazine 1,5,10-trimethyl-2-phenyl-5,10-dihydrophenazine;

2,3,5,10-tetramethyl-7-trifluoromethyl-5,10-dihydrophenazine; and

2,3,5,10-tetramethyl-5,10-dihydrobenzo(B)phenazine.

53. The electrochromic mirror of claim 38, wherein said at least three electroactive species include approximately 17 millimolar of 5,10-dimethyl-5,10-dihydrophenazine, approximately 8.5 millimolar of 2-phenyl-5,10-dimethyl-5,10-dihydrophenazine, approximately 4.3 millimolar of 2,3-diphenyl-5,10-dimethyl-5,10-dihydrophenazine, approximately 17 millimolar of 1,1'"'"'-dibenzyl-2,2'"'"',6,6'"'"'-tetramethyl-4,4'"'"'-dipyridinium bis(tetrafluoroborate), and approximately 17 millimolar of 1,1'"'"'-ethylene-4,4'"'"'-dimethyl-2,2'"'"'-dipyridinium bis(hexafluorophosphate).

54. The electrochromic mirror of claim 38, wherein said at least three electroactive species include approximately 17 millimolar of 5,10-dimethyl-5,10-dihydrophenazine, approximately 8.5 millimolar of 2-phenyl-5,10-dimethyl-5,10-dihydrophenazine, approximately 4.3 millimolar of 2,3-diphenyl-5,10-dimethyl-5,10-dihydrophenazine, approximately 19 millimolar of 1,1'"'"'-dibenzyl-2,2'"'"',6,6'"'"'-tetramethyl4,4'"'"'-dipyridinium bis(tetrafluoroborate), and approximately 15 millimolar of 1,1'"'"'-ethylene-4,4'"'"'-dimethyl-2,2'"'"'-dipyridinium bis(hexafluorophosphate).

55. The electrochromic mirror of claim 38, wherein said pre-selected color is a member of the group consisting of red, yellow, green, blue, purple, and gray.

56. The electrochromic mirror of claim 55, wherein said pre-selected color is gray.

57. The electrochromic mirror of claim 56, wherein at least one of said electroactive materials includes a 5,10-dialkyl-5,10-dihydrophenazine where at least one of said 2, 3, 7 and 8 positions contain a member of the group consisting of:

phenyl;

substituted phenyl;

vinyl; and

phenoxy.

58. The electrochromic mirror of claim 57, wherein at least one of said electroactive materials includes a cathodic electrochromic material selected from the group consisting of salts of:

1,1'"'"'-diphenyl-4,4'"'"'-dipyridinium;

1,1'"'"'-bis(2,6-dimethylphenyl)-4,4'"'"'-dipyridinium;

1,1'"'"'-bis(3,5-dimethylphenyl)-4,4'"'"'-dipyridinium;

1-phenyl-1'"'"'-(4-dodecylphenyl)-4,4'"'"'-dipyridinium;

1,1'"'"'-bis(2,4,6-trimethylphenyl)-4,4'"'"'-dipyridinium;

1-(3,5-dimethoxyphenyl)-1'"'"'-methyl-4,4'"'"'-dipyridinium;

1-methyl-1'"'"'-phenyl-4,4'"'"'-dipyridinium;

1-methyl-1'"'"'-(2-methylphenyl)-4,4'"'"'-dipyridinium;

1-(4-methoxyphenyl)-1'"'"'-methyl-4,4'"'"'-dipyridinium;

1-methyl-1'"'"'-(2,4,6-trimethylphenyl)-4,4'"'"'-dipyridinium;

1,2,6-trimethyl-1'"'"'-phenyl-4,4'"'"'-dipyridinium;

1,1'"'"'-dimethyl-2,6-diphenyl-4,4'"'"'-dipyridinium;

1,1'"'"'-bis(3-phenyl(n-propyl))-4,4'"'"'-dipyridinium;

1,1'"'"'-dimethyl-4,4'"'"'-dipyridinium;

1,1'"'"'-dimethyl-2-(3-phenyl(n-propyl))-4,4'"'"'-dipyridinium;

1,1'"'"'-dimethyl-4,4'"'"'-(1,3,5-triazine-2,4-diyl)dipyridinium;

1,1'"'"'-dibenzyl-2,2'"'"',6,6'"'"'-tetramethyl-4,4'"'"'-dipyridinium;

1,1'"'"'-ethylene-4,4'"'"'-dimethyl-2,2'"'"'-dipyridinium; and

1,1'"'"'-dimethyl-2,2'"'"'-bis(3-phenyl(n-propyl))-4,4'"'"'-dipyridinium.

59. The electrochromic mirror of claim 56, wherein said mirror maintains a reflectance spectrum resulting in color coordinates (A/2 degree) such that C* is between zero and about 22.

60. The electrochromic mirror of claim 59, wherein said mirror maintains a reflectance spectrum resulting in color coordinates (A/2 degree) such that a* is between zero and about -18.

74. The electrochromic mirror according to claims 38 and 61, wherein said electrochromic medium is gray and wherein said transparent conductor on said rear surface of front element is color suppressed.

75. The electrochromic device according to claim 74, wherein said reflector is white.

61. An electrochromic variable reflectance mirror for automotive vehicles, comprising:

front and rear spaced elements each having front and rear surfaces;

a layer of transparent conductive material disposed on said rear surface of said front element;

a reflector disposed on one side of said rear element provided that, if said reflector is on said rear surface of said rear element, then said front surface of said rear element contains a layer of a transparent conductive material; and

a perimeter sealing member bonding together said front and rear spaced elements in a spaced-apart relationship to define a chamber therebetween;

where said chamber contains an electrochromic medium, said electrochromic medium comprising at least three electroactive materials, at least two of which are electrochromic, where the redox potentials of all of said electroactive materials that are anodic are within about 200 mV of one another, and wherein the redox potentials of all of said electroactive materials that are cathodic are within about 200 mV of one another.

62. The electrochromic mirror of claim 61, wherein the redox potentials of all of said electroactive materials that are anodic are within 60 mV of one another, and wherein the redox potentials of all of said electroactive materials that are cathodic are within 60 mV of one another.

63. The electrochromic mirror of claim 62, wherein the redox potentials of all of said electroactive materials that are anodic are within 40 mV of one another, and wherein the redox potentials of all of said electroactive materials that are cathodic are within 40 mV of one another.

64. The electrochromic mirror of claim 61, wherein said at least three electroactive species include at least one cathodic material selected from the group consisting of salts of:

1,1'"'"'-diphenyl-4,4'"'"'-dipyridinium;

1,1'"'"'-bis(2,6-dimethylphenyl)-4,4'"'"'-dipyridinium;

1,1'"'"'-bis(3,5-dimethylphenyl)-4,4'"'"'-dipyridinium;

1-phenyl-1'"'"'-(4-dodecylphenyl)-4,4'"'"'-dipyridinium;

1,1'"'"'-bis(2,4,6-trimethylphenyl)-4,4'"'"'-dipyridinium;

1-(3,5-dimethoxyphenyl)-1'"'"'-methyl-4,4'"'"'-dipyridinium;

1-methyl-1'"'"'-phenyl-4,4'"'"'-dipyridinium;

1-methyl-1'"'"'-(2-methylphenyl)-4,4'"'"'-dipyridinium;

1-(4-methoxyphenyl)-1'"'"'-methyl-4,4'"'"'-dipyridinium;

1-methyl-1'"'"'-(2,4,6-trimethylphenyl)-4,4'"'"'-dipyridinium;

1,2,6-trimethyl-1'"'"'-phenyl-4,4'"'"'-dipyridinium;

1,1'"'"'-dimethyl-2,6-diphenyl-4,4'"'"'-dipyridinium;

1,1'"'"'-bis(3-phenyl(n-propyl))-4,4'"'"'-dipyridinium;

1,1'"'"'-dimethyl-4,4'"'"'-dipyridinium;

1,1'"'"'-dimethyl-2-(3-phenyl(n-propyl))-4,4'"'"'-dipyridinium;

1,1'"'"'-dimethyl-4,4'"'"'-(1,3,5-triazine-2,4-diyl)dipyridinium;

1,1'"'"'-dibenzyl-2,2'"'"',6,6'"'"'-tetramethyl-4,4'"'"'-dipyridinium;

1,1'"'"'-ethylene-4,4'"'"'-dimethyl-2,2'"'"'-dipyridinium; and

1,1'"'"'-dimethyl-2,2'"'"'-bis(3-phenyl(n-propyl))-4,4'"'"'-dipyridinium, and wherein said at least three electroactive species include at least one anodic material selected from the group consisting of;

N,N,N'"'"',N'"'"'-tetramethyl-p-phenylenediamine;

2,5,10-trimethyl-3-phenyl-5,10-dihydrophenazine;

5-ethyl-10-methyl-5,10-dihydrophenazine;

5,10-dimethyl-5,10-dihydrobenzo(A)phenazine;

2,7-diphenoxy-5,10-dimethyl-5,10-dihydrophenazine;

2-phenoxy-5,10-dimethyl-5,10-dihydrophenazine;

2,7-bis(o-tolyl)-5,10-dimethyl-5,10-dihydrophenazine;

2,3-dimethyl-7-trifluoromethyl-5,10-diethyl-5,10-dihydrophenazine;

5,10-dimethyl-5,10-dihydrophenazine;

2,3-diphenyl-5,10-dimethyl-5,10-dihydrophenazine;

2,7-diphenyl-5,10-dimethyl-5,10-dihydrophenazine;

2-vinyl-5,10-dimethyl-5,10-dihydrophenazine;

2-phenyl-5,10-dimethyl-5,10-dihydrophenazine;

5,10-diisopropyl-5,10-dihydrophenazine;

5,10-dimethyl-5,10-dihydrodibenzo(A,C)phenazine 1,5,10-trimethyl-2-phenyl5,10-dihydrophenazine;

2,3,5,10-tetramethyl-7-trifluoromethyl-5,10-dihydrophenazine; and

2,3,5,10-tetramethyl-5,10-dihydrobenzo(B)phenazine.

65. The electrochromic mirror of claim 61, wherein said at least three electroactive species include approximately 17 millimolar of 5,10-dimethyl-5,10-dihydrophenazine, approximately 8.5 millimolar of 2-phenyl-5,10-dimethyl-5,10-dihydrophenazine, approximately 4.3 millimolar of 2,3-diphenyl-5,10-dimethyl-5,10-dihydrophenazine, approximately 17 millimolar of 1,1'"'"'-dibenzyl-2,2'"'"',6,6'"'"'-tetramethyl-4,4'"'"'-dipyridinium bis(tetrafluoroborate), and approximately 17 millimolar of 1,1'"'"'-ethylene-4,4'"'"'-dimethyl-2,2'"'"'-dipyridinium bis(hexafluorophosphate).

66. The electrochromic mirror of claim 61, wherein said at least three electroactive species include approximately 17 millimolar of 5,10-dimethyl-5,10-dihydrophenazine, approximately 8.5 millimolar of 2-phenyl-5,10-dimethyl5,10-dihydrophenazine, approximately 4.3 millimolar of 2,3-diphenyl-5,10-dimethyl-5,10-dihydrophenazine, approximately 19 millimolar of 1,1'"'"'-dibenzyl-2,2'"'"',6,6'"'"'-tetramethyl-4,4'"'"'-dipyridinium bis(tetrafluoroborate), and approximately 15 millimolar of 1,1'"'"'-ethylene-4,4'"'"'-dimethyl-2,2'"'"'-dipyridinium bis(hexafluorophosphate).

67. The electrochromic mirror of claim 61, wherein said pre-selected perceived color is a member of the group consisting of red, yellow, green, blue, purple, and gray.

68. The electrochromic mirror of claim 67, wherein said pre-selected color is gray.

69. The electrochromic mirror of claim 68, wherein at least one of said electroactive materials includes a 5,10-dialkyl-5,10-dihydrophenazine where at least one of said 2, 3, 7 and 8 positions contain a member of the group consisting of:

phenyl;

substituted phenyl;

vinyl; and

phenoxy.

70. The electrochromic mirror of claim 68, wherein at least one of said electroactive materials includes a cathodic electrochromic material selected from the group consisting of salts of:

1,1'"'"'-diphenyl-4,4'"'"'-dipyridinium;

1,1'"'"'-bis(2,6-dimethylphenyl)-4,4'"'"'-dipyridinium;

1,1'"'"'-bis(3,5-dimethylphenyl)-4,4'"'"'-dipyridinium;

1-phenyl-1'"'"'-(4-dodecylphenyl)-4,4'"'"'-dipyridinium;

1,1'"'"'-bis(2,4,6-trimethylphenyl)-4,4'"'"'-dipyridinium;

1-(3,5-dimethoxyphenyl)-1'"'"'-methyl-4,4'"'"'-dipyridinium;

1-methyl-1'"'"'-phenyl-4,4'"'"'-dipyridinium;

1-methyl-1'"'"'-(2-methylphenyl)-4,4'"'"'-dipyridinium;

1-(4-methoxyphenyl)-1'"'"'-methyl-4,4'"'"'-dipyridinium;

1-methyl-1'"'"'-(2,4,6-trimethylphenyl)-4,4'"'"'-dipyridinium;

1,2,6-trimethyl-1'"'"'-phenyl-4,4'"'"'-dipyridinium;

1,1'"'"'-dimethyl-2,6-diphenyl-4,4'"'"'-dipyridinium;

1,1'"'"'-bis(3-phenyl(n-propyl))-4,4'"'"'-dipyridinium;

1,1'"'"'-dimethyl-4,4'"'"'-dipyridinium;

1,1'"'"'-dimethyl-2-(3-phenyl(n-propyl))-4,4'"'"'-dipyridinium;

1,1'"'"'-dimethyl-4,4'"'"'-(1,3,5-triazine-2,4-diyl)dipyridinium;

1,1'"'"'-dibenzyl-2,2'"'"',6,6'"'"'-tetramethyl-4,4'"'"'-dipyridinium;

1,1'"'"'-ethylene-4,4'"'"'-dimethyl-2,2'"'"'-dipyridinium; and

1,1'"'"'-dimethyl-2,2'"'"'-bis(3-phenyl(n-propyl))-4,4'"'"'-dipyridinium.

71. The electrochromic mirror of claim 68, wherein said mirror maintains a reflectance spectrum resulting in color coordinates (A/2 degree) such that C* is between zero and about 22.

72. The electrochromic mirror of claim 71, wherein said mirror maintains a reflectance spectrum resulting in color coordinates (A/2 degree) such that a* is between zero and about -18.

76. An electrochromic device, comprising:

front and rear spaced elements each having front and rear surfaces;

a layer of transparent conductive material disposed on said rear surface of said front element and said front surface of said rear element, and a perimeter sealing member bonding together said front and rear spaced elements in a spaced-apart relationship to define a chamber therebetween; and

where said chamber contains an electrochromic medium, said electrochromic medium comprising at least three electroactive materials, at least two of which are electrochromic, whose concentrations are chosen to produce a pre-selected perceived color, where said device does not exhibit staging.

77. An electrochromic device, comprising:

front and rear spaced elements each having front and rear surfaces;

a layer of transparent conductive material disposed on said rear surface of said front element and said front surface of said rear element, and a perimeter sealing member bonding together said front and rear spaced elements in a spaced-apart relationship to define a chamber therebetween; and

where said chamber contains an electrochromic medium, said electrochromic medium comprising at least three electroactive materials, at least two of which are electrochromic, wherein said device maintains a transmittance spectrum resulting in color coordinates (D₆₅ /2 degrees) such that C* is between zero and about 22.

78. The electrochromic device of claim 77, wherein said device maintains a transmittance spectrum resulting in color coordinates (D₆₅ /2 degree) such that a* is between zero and about -18.

79. An electrochromic device, comprising:

front and rear spaced elements each having front and rear surfaces;

a layer of transparent conductive material disposed on said rear surface of said front element and said front surface of said rear element, and a perimeter sealing member bonding together said front and rear spaced elements in a spaced-apart relationship to define a chamber therebetween; and

where said chamber contains an electrochromic medium, said electrochromic medium comprising at least three electroactive materials, at least two of which are anodic electrochromic compounds and at least one is a generally colorless cathodic electroactive compound in two oxidation states.

80. The electrochromic device of claim 79, wherein said anodic electrochromic compounds are surface confined.

81. The electrochromic device of claim 79, wherein said chamber further includes a member of the group consisting of a light absorber, a light stabilizer, a thermal stabilizer, an antioxidant, a thickener or a free standing gel.

82. An electrochromic device, comprising:

front and rear spaced elements each having front and rear surfaces;

a layer of transparent conductive material disposed on said rear surface of said front element and said front surface of said rear element, and a perimeter sealing member bonding together said front and rear spaced elements in a spaced-apart relationship to define a chamber therebetween; and

where said chamber contains an electrochromic medium, said electrochromic medium comprising at least three electroactive materials, at least two of which are cathodic compounds and at least one is a generally colorless anodic electroactive compound in two oxidation states.

83. The electrochromic device of claim 82, wherein said cathodic electrochromic compounds are surface confined.

84. The electrochromic device of claim 82 wherein said chamber further includes a member of the group consisting of a light absorber, a light stabilizer, a thermal stabilizer, an antioxidant, a thickener or a free standing gel.