Substituted metallocenes and electrochromic media and devices comprising the same

• US 6,594,066 B2
• Filed: 04/22/2002
• Issued: 07/15/2003
• Est. Priority Date: 02/24/2000
• Status: Active Grant

• Current Assignee: Gentex Corporation
• Original Assignee: Gentex Corporation
• Inventors: Guarr, Thomas F., Lomprey, Jeffrey R.
• Primary Examiner(s): Epps, Georgia
• Assistant Examiner(s): THOMPSON, TIMOTHY J
• Application Number:
  US10/121,760
• Publication Number:
  US 20030039020A1
• Time in Patent Office: 449 Days
• Field of Search: 359/265, 359/272, 359/273, 359/275, 359/321, 359/322, 252/583, 544/37
• US Class Current: 359/265
• CPC Class Codes: C07F 17/02 of metals of Groups 8, 9 or 10 of the Periodic System
• 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

Abstract

An electrochromic device comprising at least one substantially transparent substrate having an electrically conductive material associated therewith, and an electrochromic medium which comprises a solvent, a cathodic material, and an anodic electrochromic material represented by the formula:

wherein R₁-R₁₀ are the same or different and at least three of R₁-R₁₀ are the same or different and comprise a straight or branched alkyl, aryl, alkaryl, or aralkyl group containing approximately 1 to approximately 40 carbon atom(s), and/or a silyl or siloxyl group containing approximately 1 to approximately 40 silicon atom(s), wherein the carbon or silicon atom(s) may be a linking group to, or part of, one or more functional groups comprising nitrites; nitro constituents; sulfoxides; sulfonates; phosphonium constituents; phosphonates; phosphonites; ammonium constituents; viologens, including bipyridinyl constituents; carbonyls, including carbonates, carbamates; ketones; esters; and amides; ethers, including polyethers; amines, including tertiary amines; alkenes; alkynes; and mixtures thereof; wherein any remainder of R₁-R₁₀ comprise H; and wherein M comprises a transition metal.

Claims

1. An electrochromic device, comprising:

a first substantially transparent substrate having an electrically conductive material associated therewith;

a second substrate having an electrically conductive material associated therewith; and

an electrochromic medium contained within a chamber positioned between the first and second substrates which comprises a material represented by the formula;

 

wherein R₁-R₁₀ are the same or different and at least three of R₁-R₁₀ are the same or different and comprise a straight or branched alkyl, aryl, alkaryl, or aralkyl group containing approximately 1 to approximately 40 carbon atom(s), and/or a silyl or siloxyl group containing approximately 1 to approximately 40 silicon atom(s), wherein the carbon or silicon atom(s) may be a linking group to, or part of, one or more functional groups comprising nitrites;

nitro constituents;

sulfoxides;

sulfonates;

phosphonium constituents;

phosphonates;

phosphonites;

ammonium constituents;

viologens, including bipyridinyl constituents;

carbonyls, including carbonates, carbamates, ketones, esters, and amides;

ethers, including polyethers;

amines, including tertiary amines;

alkenes;

alkynes; and

mixtures thereof;

wherein any remainder of R₁-R₁₀ comprise H; and

wherein M comprises a transition metal in any available oxidation state.

2. The electrochromic device according to claim 1, wherein R₁-R₁₀ are the same or different and at least four of R₁-R₁₀ are the same or different and comprise a straight or branched alkyl, aryl, alkaryl, or aralkyl group containing approximately 1 to approximately 40 carbon atom(s), and/or a silyl or siloxyl group containing approximately 1 to approximately 40 silicon atom(s), wherein the carbon or silicon atom(s) may be a linking group to, or part of, one or more functional groups comprising nitriles;

nitro constituents;

sulfoxides;

sulfonates;

phosphonium constituents;

phosphonates;

phosphonites;

ammonium constituents;

viologens, including bipyridinyl constituents;

carbonyls, including carbonates, carbamates, ketones, esters, and amides;

ethers, including polyethers;

amines, including tertiary amines;

alkenes;

alkynes; and

mixtures thereof;

wherein any remainder of R₁-R₁₀ comprise H; and

wherein M comprises a transition metal in any available oxidation state.

3. The electrochromic device according to claim 2, wherein at least two of R₁-R₅ are the same or different and at least two of R₆-R₁₀ are the same or different and comprise a straight or branched alkyl, aryl, alkaryl, or aralkyl group containing approximately 1 to approximately 40 carbon atom(s), and/or a silyl or siloxyl group containing approximately 1 to approximately 40 silicon atom(s), wherein the carbon or silicon atom(s) may be a linking group to, or part of, one or more functional groups comprising nitriles;

nitro constituents;

sulfoxides;

sulfonates;

phosphonium constituents;

phosphonates;

phosphonites;

ammonium constituents;

viologens, including bipyridinyl constituents;

carbonyls, including carbonates, carbamates, ketones, esters, and amides;

ethers, including polyethers;

amines, including tertiary amines;

alkenes;

alkynes; and

mixtures thereof.

4. The electrochromic device according to claim 3, wherein two of R₁-R₅ are the same or different and two of R₆-R₁₀ are the same or different and comprise a straight or branched alkyl, aryl, alkaryl, or aralkyl group containing approximately 1 to approximately 40 carbon atom(s), wherein the carbon atom(s) may be a linking group to one or more ammonium constituents.

5. The electrochromic device according to claim 4, wherein one of R₁-R₅ is linked to an ammonium constituent.

6. The electrochromic device according to claim 1, wherein R₁-R₁₀ are the same or different and at least four of R₁-R₁₀ are the same or different and comprise a straight or branched alkyl, aryl, alkaryl, or aralkyl group containing 1 to 40 carbon atoms, and/or a silyl or siloxyl group containing 1 to 40 silicon atoms, wherein the carbon or silicon atoms may be a linking group to, or part of, one or more functional groups comprising nitrites;

nitro constituents;

sulfoxides;

sulfonates;

phosphonium constituents;

phosphonates;

phosphonites;

ammonium constituents;

viologens, including bipyridinyl constituents;

carbonyls, including carbonates, carbamates, ketones, esters, and amides;

ethers, including polyethers;

amines, including tertiary amines;

alkenes;

alkynes; and

mixtures thereof;

wherein any remainder of R₁-R₁₀ comprise H; and

wherein M comprises a transition metal in any available oxidation state.

7. The electrochromic device according to claim 6, wherein M comprises Fe.

8. The electrochromic device according to claim 1, wherein M comprises Fe.

9. The electrochromic device according to claim 1, further comprising a cross-linked polymer matrix or a free standing gel.

10. The electrochromic device according to claim 1, wherein the electrochromic medium comprises 1,1′

,2,2′

,3,3′

,4,4′

,5,5′

-decamethylferrocene.

11. The electrochromic device according to claim 10, wherein the electrochromic medium further comprises 1,1′

,2,2′

,3,3′

,4,4′

,5,5′

-decamethylferrocinium tetrafluoroborate.

12. The electrochromic device according to claim 1, wherein the electrochromic medium comprises 1,1′

,2,2′

,3,3′

,4,4′

,5,5′

-decamethylferrocinium tetrafluoroborate.

13. An electrochromic device, comprising:

a first substantially transparent substrate having an electrically conductive material associated therewith;

a second substrate having an electrically conductive material associated therewith; and

an electrochromic medium contained within a chamber positioned between the first and second substrates which comprises a metallocene, wherein the metallocene comprises at least three substituents which serve to increase stability of the metallocene relative to the stability of the metallocene without the at least three substituents.

14. The electrochromic device according to claim 13, wherein the metallocene comprises a substituted ferrocene.

15. The electrochromic device according to claim 13, wherein the at least three substituents are the same or different and comprise a straight or branched alkyl, aryl, alkaryl, or aralkyl group containing approximately 1 to approximately 40 carbon atom(s), and/or a silyl or siloxyl group containing approximately 1 to approximately 40 silicon atom(s), wherein the carbon or silicon atom(s) may be a linking group to, or part of, one or more functional groups comprising nitrites;

nitro constituents;

sulfoxides;

sulfonates;

phosphonium constituents;

phosphonates;

phosphonites;

ammonium constituents;

viologens, including bipyridinyl constituents;

carbonyls, including carbonates, carbamates, ketones, esters, and amides;

ethers, including polyethers;

amines, including tertiary amines;

alkenes;

alkynes; and

mixtures thereof.

16. An electrochromic device, comprising:

a first substantially transparent substrate having an electrically conductive material associated therewith;

a second substrate having an electrically conductive material associated therewith;

an electrochromic medium contained within a chamber positioned between the first and second substrates which comprises a metallocene, wherein the metallocene comprises at least four substituents which serve to increase stability of the metallocene relative to the stability of the metallocene without the at least four substituents.

17. An electrochromic medium for use in an electrochromic device, comprising:

a material represented by the formula;

wherein R₁-R₁₀ are the same or different and at least three of R₁-R₁₀ are the same or different and comprise a straight or branched alkyl, aryl, alkaryl, or aralkyl group containing approximately 1 to approximately 40 carbon atom(s), and/or a silyl or siloxyl group containing approximately 1 to approximately 40 silicon atom(s), wherein the carbon or silicon atom(s) may be a linking group to, or part of, one or more functional groups comprising nitrites;

nitro constituents;

sulfoxides;

sulfonates;

phosphonium constituents;

phosphonates;

phosphonites;

ammonium constituents;

viologens, including bipyridinyl constituents;

carbonyls, including carbonates, carbamates, ketones, esters, and amides;

ethers, including polyethers;

amines, including tertiary amines;

alkenes;

alkynes; and

mixtures thereof;

wherein any remainder of R₁-R₁₀ comprise H; and

wherein M comprises a transition metal in any available oxidation state.

18. The electrochromic medium according to claim 17, wherein R₁-R₁₀ are the same or different and at least four of R₁-R₁₀ are the same or different and comprise a straight or branched alkyl, aryl, alkaryl, or aralkyl group containing approximately 1 to approximately 40 carbon atom(s), and/or a silyl or siloxyl group containing approximately 1 to approximately 40 silicon atom(s), wherein the carbon or silicon atom(s) may be a linking group to, or part of, one or more functional groups comprising nitrites;

nitro constituents;

sulfoxides;

sulfonates;

phosphonium constituents;

phosphonates;

phosphonites;

ammonium constituents;

viologens, including bipyridinyl constituents;

carbonyls, including carbonates, carbamates, ketones, esters, and amides;

ethers, including polyethers;

amines, including tertiary amines;

alkenes;

alkynes; and

mixtures thereof;

wherein any remainder of R₁-R₁₀ comprise H; and

wherein M comprises a transition metal in any available oxidation state.

19. The electrochromic medium according to claim 18, wherein at least two of R₁-R₅ are the same or different and at least two of R₆-R₁₀ are the same or different and comprise a straight or branched alkyl, aryl, alkaryl, or aralkyl group containing approximately 1 to approximately 40 carbon atom(s), and/or a silyl or siloxyl group containing approximately 1 to approximately 40 silicon atom(s), wherein the carbon or silicon atom(s) may be a linking group to, or part of, one or more functional groups comprising nitrites;

nitro constituents;

sulfoxides;

sulfonates;

phosphonium constituents;

phosphonates;

phosphonites;

ammonium constituents;

viologens, including bipyridinyl constituents;

carbonyls, including carbonates, carbamates, ketones, esters, and amides;

ethers, including polyethers;

amines, including tertiary amines;

alkenes;

alkynes; and

mixtures thereof.

20. The electrochromic medium according to claim 19, wherein two of R₁-R₅ are the same or different and two of R₆-R₁₀ are the same or different and comprise a straight or branched alkyl, aryl, alkaryl, or aralkyl group containing approximately 1 to approximately 40 carbon atom(s), wherein the carbon atom(s) may be a linking group to one or more ammonium constituents.

21. The electrochromic medium according to claim 20, wherein one of R₁-R₅ is linked to an ammonium constituent.

22. The electrochromic medium according to claim 17, wherein R₁-R₁₀ are the same or different and at least four of R₁-R₁₀ are the same or different and comprise a straight or branched alkyl, aryl, alkaryl, or aralkyl group containing 1 to 40 carbon atoms, and/or a silyl or siloxyl group containing 1 to 40 silicon atoms, wherein the carbon or silicon atoms may be a linking group to, or part of, one or more functional groups comprising nitrites;

nitro constituents;

sulfoxides;

sulfonates;

phosphonium constituents;

phosphonates;

phosphonites;

ammonium constituents;

viologens, including bipyridinyl constituents;

carbonyls, including carbonates, carbamates, ketones, esters, and amides;

ethers, including polyethers;

amines, including tertiary amines;

alkenes;

alkynes; and

mixtures thereof;

wherein any remainder of R₁-R₁₀ comprise H; and

wherein M comprises a transition metal in any available oxidation state.

23. The electrochromic medium according to claim 22, wherein M comprises Fe.

24. The electrochromic medium according to claim 17, further comprising a cross-linked polymer matrix or a free standing gel.

25. An electrochromic medium for use in an electrochromic device, comprising:

a metallocene, wherein the metallocene comprises at least three substituents which serve to increase stability of the metallocene relative to the stability of the metallocene without the at least three substituents.

26. The electrochromic medium according to claim 25, wherein the metallocene comprises a substituted ferrocene.

27. The electrochromic medium according to claim 25, wherein the at least three substituents are the same or different and comprise a straight or branched alkyl, aryl, alkaryl, or aralkyl group containing approximately 1 to approximately 40 carbon atom(s), and/or a silyl or siloxyl group containing approximately 1 to approximately 40 silicon atom(s), wherein the carbon or silicon atom(s) may be a linking group to, or part of, one or more functional groups comprising nitrites;

nitro constituents;

sulfoxides;

sulfonates;

phosphonium constituents;

phosphonates;

phosphonites;

ammonium constituents;

viologens, including bipyridinyl constituents;

carbonyls, including carbonates, carbamates, ketones, esters, and amides;

ethers, including polyethers;

amines, including tertiary amines;

alkenes;

alkynes; and

mixtures thereof.

28. A material for use in an electrochromic device represented by the formula:

wherein R₁-R₁₀ are the same or different and at least three of R₁-R₁₀ are the same or different and comprise a straight or branched alkyl, aryl, alkaryl, or aralkyl group containing approximately 1 to approximately 40 carbon atom(s), and/or a silyl or siloxyl group containing approximately 1 to approximately 40 silicon atom(s), wherein the carbon or silicon atom(s) may be a linking group to, or part of, one or more functional groups comprising nitrites;

nitro constituents;

sulfoxides;

sulfonates;

phosphonium constituents;

phosphonates;

phosphonites;

ammonium constituents;

viologens, including bipyridinyl constituents;

carbonyls, including carbonates, carbamates, ketones, esters, and amides;

ethers, including polyethers;

amines, including tertiary amines;

alkenes;

alkynes; and

mixtures thereof;

wherein any remainder of R₁-R₁₀ comprise H; and

wherein M comprises a transition metal in any available oxidation state.

29. The material according to claim 28, wherein R₁-R₁₀ are the same or different and at least four of R₁-R₁₀ are the same or different and comprise a straight or branched alkyl, aryl, alkaryl, or aralkyl group containing approximately 1 to approximately 40 carbon atom(s), and/or a silyl or siloxyl group containing approximately 1 to approximately 40 silicon atom(s), wherein the carbon or silicon atom(s) may be a linking group to one or more functional groups comprising nitrites;

nitro constituents;

sulfoxides;

sulfonates;

phosphonium constituents;

phosphonates;

phosphonites;

ammonium constituents;

viologens, including bipyridinyl constituents;

carbonyls, including carbonates, carbamates, ketones, esters, and amides;

ethers, including polyethers;

amines, including tertiary amines;

alkenes;

alkynes; and

mixtures thereof;

wherein any remainder of R₁-R₁₀ comprise H; and

wherein M comprises a transition metal in any available oxidation state.

30. The material according to claim 29, wherein at least two of R₁-R₅ are the same or different and at least two of R₆-R₁₀ are the same or different and comprise a straight or branched alkyl, aryl, alkaryl, or aralkyl group containing approximately 1 to approximately 40 carbon atom(s);

and/or a silyl or siloxyl group containing approximately 1 to approximately 40 silicon atom(s), wherein the carbon or silicon atom(s) may be a linking group to, or part of, one or more functional groups comprising nitrites;

nitro constituents;

sulfoxides;

sulfonates;

phosphonium constituents;

phosphonates;

phosphonites;

ammonium constituents;

viologens, including bipyridinyl constituents;

carbonyls, including carbonates;

carbamates;

ketones;

esters; and

amides;

ethers, including polyethers;

amines, including tertiary amines;

alkenes;

alkynes; and

mixtures thereof.

31. The material according to claim 30, wherein two of R₁-R₅ are the same or different and two of R₆-R₁₀ are the same or different and comprise a straight or branched alkyl, aryl, alkaryl, or aralkyl group containing approximately 1 to approximately 40 carbon atom(s), wherein the carbon atom(s) may be a linking group to one or more ammonium constituents.

32. The material according to claim 31, wherein one of R₁-R₅ is linked to an ammonium constituent.

33. The material according to claim 28, wherein R₁-R₁₀ are the same or different and at least four of R₁-R₁₀ are the same or different and comprise a straight or branched alkyl, aryl, alkaryl, or aralkyl group containing 1 to 40 carbon atoms, and/or a silyl or siloxyl group containing 1 to 40 silicon atoms, wherein the carbon or silicon atoms may be a linking group to, or part of, one or more functional groups comprising nitrites;

nitro constituents;

sulfoxides;

sulfonates;

phosphonium constituents;

phosphonates;

phosphonites;

ammonium constituents;

viologens, including bipyridinyl constituents;

carbonyls, including carbonates, carbamates, ketones, esters, and amides;

ethers, including polyethers;

amines, including tertiary amines;

alkenes;

alkynes; and

mixtures thereof, wherein any remainder of R₁-R₁₀ comprise H; and

wherein M comprises a transition metal in any available oxidation state.

34. The material according to claim 33, wherein M comprises Fe.

35. An electrochromic device, comprising:

a first substantially transparent substrate having an electrically conductive material associated therewith;

a second substrate having an electrically conductive material associated therewith; and

an electrochromic medium contained within a chamber positioned between the first and second substrates which comprises a material represented by the formula;

wherein M comprises a transition metal in any available oxidation state;

wherein X₁-X₁₀ are the same or different and comprise C, Si, or H;

wherein R_n1-R_n10 are the same or different and comprise O, C, or a straight or branched alkyl, aryl, alkaryl, or aralkyl group containing approximately 1 to approximately 40 carbon atom(s), wherein the carbon atom(s) may be a linking group to, or part of, one or more functional groups comprising nitriles;

nitro constituents;

sulfoxides;

sulfonates;

phosphonium constituents;

phosphonates;

phosphonites;

ammonium constituents;

viologens, including bipyridinyl constituents;

carbonyls, including carbonates, carbamates, ketones, esters, and amides;

ethers, including polyethers;

amines, including tertiary amines;

alkenes;

alkynes; and

mixtures thereof;

wherein n₁-n₁₀ are the same or different and comprise 0, 1, 2, or 3, and are the number of bonds between a given X and associated constituent(s) other than hydrogen;

wherein Z₁-Z₁₀ are the same or different and comprise 0 or 1;

and wherein $\underset{y=1}{\overset{10}{\sum <br><br>}}<br><br>\text{\hspace{1em}<br><br>}<br><br>n_y\ge <br><br>7;<br><br>\underset{y=1}{\overset{10}{\sum <br><br>}}<br><br>\text{\hspace{1em}<br><br>}<br><br>z_y\ge <br><br>7;<br><br>\text{\hspace{1em}<br><br>}<br><br>\mathrm{or}<br><br>\text{\hspace{1em}<br><br>}<br><br>\underset{y=1}{\overset{10}{\sum <br><br>}}<br><br>\text{\hspace{1em}<br><br>}<br><br>\left(n_y+z_y\right)\ge <br><br>9.$

36. The electrochromic device according to claim 35, wherein $\sum _{}^{}$

y=110

 



ny≥

8;

∑

y=110

 



zy≥

8;

 



or

 



∑

y=110

 



(ny+zy)≥

10.

37. An electrochromic medium for use in an electrochromic device, comprising:

a material represented by the formula;

wherein M comprises a transition metal in any available oxidation state;

wherein X₁-X₁₀ are the same or different and comprise C, Si, or H;

wherein R_n1-R_n10 are the same or different and comprise O, C, or a straight or branched alkyl, aryl, alkaryl, or aralkyl group containing approximately 1 to approximately 40 carbon atom(s), wherein the carbon atom(s) may be a linking group to, or part of, one or more functional groups comprising nitrites;

nitro constituents;

sulfoxides;

sulfonates;

phosphonium constituents;

phosphonates;

phosphonites;

ammonium constituents;

viologens, including bipyridinyl constituents;

carbonyls, including carbonates, carbamates, ketones, esters, and amides;

ethers, including polyethers;

amines, including tertiary amines;

alkenes;

alkynes; and

mixtures thereof, wherein n₁-n₁₀ are the same or different and comprise 0, 1, 2, or 3, and are the number of bonds between a given X and associated constituent(s) other than hydrogen;

wherein Z₁-Z₁₀ are the same or different and comprise 0 or 1;

and wherein $\underset{y=1}{\overset{10}{\sum <br><br>}}<br><br>\text{\hspace{1em}<br><br>}<br><br>n_y\ge <br><br>7;<br><br>\underset{y=1}{\overset{10}{\sum <br><br>}}<br><br>\text{\hspace{1em}<br><br>}<br><br>z_y\ge <br><br>7;<br><br>\text{\hspace{1em}<br><br>}<br><br>\mathrm{or}<br><br>\text{\hspace{1em}<br><br>}<br><br>\underset{y=1}{\overset{10}{\sum <br><br>}}<br><br>\text{\hspace{1em}<br><br>}<br><br>\left(n_y+z_y\right)\ge <br><br>9.$

38. The electrochromic medium according to claim 37, wherein $\sum _{}^{}$

y=110

 



ny≥

8;

∑

y=110

 



zy≥

8;

 



or

 



∑

y=110

 



(ny+zy)≥

10.

39. A material for use in an electrochromic device represented by the formula:

wherein M comprises a transition metal in any available oxidation state;

wherein X₁-X₁₀ are the same or different and comprise C, Si, or H;

wherein R_n1-R_n10 are the same or different and comprise O, C, or a straight or branched alkyl, aryl, alkaryl, or aralkyl group containing approximately 1 to approximately 40 carbon atom(s), wherein the carbon atom(s) may be a linking group to, or part of, one or more functional groups comprising nitriles;

nitro constituents;

sulfoxides;

sulfonates;

phosphonium constituents;

phosphonates;

phosphonites;

ammonium constituents;

viologens, including bipyridinyl constituents;

carbonyls, including carbonates, carbamates, ketones, esters, and amides;

ethers, including polyethers;

amines, including tertiary amines;

alkenes;

alkynes; and

mixtures thereof;

wherein n₁-n₁₀ are the same or different and comprise 0, 1, 2, or 3, and are the number of bonds between a given X and associated constituent(s) other than hydrogen;

wherein Z₁-Z₁₀ are the same or different and comprise 0 or 1;

and wherein $\underset{y=1}{\overset{10}{\sum <br><br>}}<br><br>\text{\hspace{1em}<br><br>}<br><br>n_y\ge <br><br>7;<br><br>\underset{y=1}{\overset{10}{\sum <br><br>}}<br><br>\text{\hspace{1em}<br><br>}<br><br>z_y\ge <br><br>7;<br><br>\text{\hspace{1em}<br><br>}<br><br>\mathrm{or}<br><br>\text{\hspace{1em}<br><br>}<br><br>\underset{y=1}{\overset{10}{\sum <br><br>}}<br><br>\text{\hspace{1em}<br><br>}<br><br>\left(n_y+z_y\right)\ge <br><br>9.$

40. The material according to claim 39, wherein $\sum _{}^{}$

y=110

 



ny≥

8;

∑

y=110

 



zy≥

8;

 



or

 



∑

y=110

 



(ny+zy)≥

10.

41. An electrochromic device, comprising:

a first substantially transparent substrate having an electrically conductive material associated therewith;

a second substrate having an electrically conductive material associated therewith; and

an electrochromic medium contained within a chamber positioned between the first and second substrates which comprises a material represented by the formula;

42. The electrochromic device according to claim 41, wherein $\sum _{}^{}$

y=110

 



ny≥

8;

∑

y=110

 



zy≥

8;

 



or

 



∑

y=110

 



(ny+zy)≥

10.

43. An electrochromic medium for use in an electrochromic device, comprising:

a material represented by the formula;

44. The electrochromic medium according to claim 43, wherein $\sum _{}^{}$

y=110

 



ny≥

8;

∑

y=110

 



zy≥

8;

 



or

 



∑

y=110

 



(ny+zy)≥

10.

45. An electrochromic device, comprising:

a first substantially transparent substrate having an electrically conductive material associated therewith;

a second substrate having an electrically conductive material associated therewith; and

an electrochromic medium which comprises a material represented by the formula;

wherein R₁-R₁₀ are the same or different and at least three of R₁-R₁₀ are the same or different and comprise a straight or branched alkyl, aryl, alkaryl, or aralkyl group containing approximately 1 to approximately 40 carbon atom(s), and/or a silyl or siloxyl group containing approximately 1 to approximately 40 silicon atom(s), wherein the carbon or silicon atom(s) may be a linking group to, or part of, one or more functional groups comprising nitrites;

nitro constituents;

sulfoxides;

sulfonates;

phosphonium constituents;

phosphonates;

phosphonites;

ammonium constituents;

viologens, including bipyridinyl constituents;

carbonyls, including carbonates, carbamates, ketones, esters, and amides;

ethers, including polyethers;

amines, including tertiary amines;

alkenes;

alkynes; and

mixtures thereof;

wherein any remainder of R₁-R₁₀ comprise H; and

wherein M comprises a transition metal in any available oxidation state.

46. The electrochromic device according to claim 45, wherein the electrochromic medium comprises at least one of an anodic and cathodic material.