Near infrared-absorbing electrochromic compounds and devices comprising same

• US 6,193,912 B1
• Filed: 03/03/1998
• Issued: 02/27/2001
• Est. Priority Date: 03/03/1998
• Status: Expired due to Term

• Current Assignee: Gentex Corporation
• Original Assignee: Gentex Corporation
• Inventors: Srinivasa, Ramanujan, Baumann, Kelvin, Thieste, Dave, Byker, Harlan J.
• Primary Examiner(s): TUCKER, PHILIP C
• Application Number:
  US09/034,531
• Time in Patent Office: 1,092 Days
• Field of Search: 252/583, 359/265, 359/267, 359/272, 359/273, 359/275
• US Class Current: 252/583
• 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

Electrochromic compounds capable of reversibly attenuating the transmittance of the near infrared portion of the electromagnetic spectrum are provided. These compounds exhibit an energy difference between the singly occupied molecular orbital (SOMO) energy and the highest doubly occupied molecular orbital (HDOMO) energy (E_SOMO−E_HDOMO) of less than about 3.6 eV. In addition, these compounds have a transition moment of the configuration made up of the HDOMO and SOMO that is “long axis polarized”.

Claims

1. An electrochromic medium comprising at least one solution-phase anodic compound, where an oxidized form of said anodic compound has a E_SOMO−

E_HDOMO of less than 3.6 eV, a redox potential greater than about 90 mV, and an absorption band having a λ

_max greater than approximately 750 nm, excluding therefrom the compounds of the formula;

wherein R₅₁ and R₅₄ are the same or different and are each selected from hydrogen and dialkylamino, wherein the alkyl groups are the same or different and are each of 1 to 6 carbon atoms, R₅₂ is oxygen, sulfur or NR₅₅, wherein R₅₅ is the same as or different from R₅₃ and both R₅₅ and R₅₃ are selected from hydrogen, alkyl of 1 to 10 carbon atoms, phenyl optionally substituted at any one position with chloride, bromide, iodide, cyano, or alkyl of 1 to 4 carbon atoms, or benzyl, optionally substituted at any one position of the phenyl group with chloride, bromide, iodide, cyano, or alkyl of 1 to 4 carbon atoms.

2. The medium of claim 1, wherein said oxidized form of said anodic compound is capable of absorbing in the NIR portion of the electromagnetic spectrum.

3. The medium of claim 1, wherein said medium is self-erasing.

4. The medium of claim 1, wherein said medium is solution-phase.

5. The medium of claim 1, wherein the outer product of the SOMO and HDOMO of said anodic compound results in a long axis transition dipole moment.

6. The medium of claim 5, wherein said oxidized form of said anodic compound is capable of absorbing in the NIR portion of the electromagnetic spectrum and where said electrochromic medium further comprises a solvent and a cathodic electrochromic material.

7. The medium of claim 6, wherein said medium is self-erasing.

8. The medium of claim 6, wherein said medium is solution-phase.

9. The medium of claim 6, wherein said anodic electrochromic compound is selected from the group consisting of:

10. An electrochromic device, which comprises, as the medium of reversibly variable transmittance to light, the electrochromic medium of claim 1.

11. An electrochromic device, which comprises, as the medium of reversibly variable transmittance to light, the electrochromic medium of claim 5.

12. The device of claim 11, wherein said electrochromic medium is held in a space defined by two planar, parallel, spaced-apart walls, and a periphery defined by a seal, where the side of each of said walls that is in contact with said medium is coated with a layer of electrically conductive material.

13. An electrochromic medium comprising at least one solution-phase anodic compound, where an oxidized form of said anodic compound has an E_SOMO−

E_HDOMO of less than 3.6 eV, and an absorption band having a λ

_max greater than approximately 750 nm, excluding therefrom the compounds of the formula;

wherein R₇₆ is oxygen or sulfur, R₈₀ is hydrogen or dialkylamino, wherein the alkyl groups are the same or different and are each of 1 to 6 carbon atoms, and R₇₇ and R₇₈ are the same or different and are each selected from hydrogen, alkyl of 1 to 6 carbon atoms, phenyl optionally substituted at any one position with an alkyl group of 1 to 6 carbon atoms, and benzyl, optionally substituted at any one position of the phenyl group with an alkyl group of 1 to 6 carbon atoms, and excluding therefrom the compounds of the formula;

wherein R₅₁ and R₅₄ are the same or different and are each selected from hydrogen and dialkylamino, wherein the alkyl groups are the same or different and are each of 1 to 6 carbon atoms;

R₅₂ is oxygen, sulfur or NR₅₅, wherein R₅₅ is the same as or different from R₅₃ and both R₅₅ and R₅₃ are selected from hydrogen, alkyl of 1 to 10 carbon atoms, phenyl optionally substituted at any one position with chloride, bromide, iodide, cyano, or alkyl of 1 to 4 carbon atoms, or benzyl, optionally substituted at any one position of the phenyl group with chloride, bromide, iodide, cyano, or alkyl of 1 to 4 carbon atoms.

14. The medium of claim 13, wherein said oxidized form of said anodic compound is capable of absorbing in the NIR portion of the electromagnetic spectrum.

15. The medium of claim 14, wherein said medium is self-erasing.

16. The medium of claim 15, wherein said medium is solution-phase.

17. The medium of claim 13, wherein the outer product of the SOMO and HDOMO of said anodic compound results in a long axis transition dipole moment.

18. The medium of claim 17, wherein, said oxidized form of said anodic compound is capable of absorbing in the NIR portion of the electromagnetic spectrum and where said electrochromic medium further comprises a solvent and a cathodic electrochromic material.

19. The medium of claim 18, wherein said medium is self-erasing.

20. The medium of claim 18, wherein said medium is solution-phase.

21. The medium of claim 18, wherein said anodic electrochromic compound is selected from the group consisting of:

22. An electrochromic device, which comprises, as the medium of reversibly variable transmittance to light, the electrochromic medium of claim 15.

23. An electrochromic device, which comprises, as the medium of reversibly variable transmittance to light, the electrochromic medium of claim 18.

24. The device of claim 23, wherein said electrochromic medium is held in a space defined by two planar, parallel, spaced-apart walls, and a periphery defined by a seal, where the side of each of said walls that is in contact with said medium is coated with a layer of electrically conductive material.

25. An electrochromic medium comprising a crosslinked polymer matrix and at least one anodic compound, where an oxidized form of said anodic compound has a redox potential greater than about 90 mV, and an absorption band having a λ

_max greater than approximately 750 nm, excluding therefrom the compounds of the formula;

wherein R₅₁ and R₅₄ are the same or different and are each selected from hydrogen and dialkylamino, wherein the alkyl groups are the same or different and are each of 1 to 6 carbon atoms;

R₅₂ is oxygen, sulfur or NR₅₅, wherein R₅₅ is the same as or different from R₅₃ and both R₅₅ and R₅₃ are selected from hydrogen, alkyl of 1 to 10 carbon atoms, phenyl optionally substituted at any one position with chloride, bromide, iodide, cyano, or alkyl of 1 to 4 carbon atoms, or benzyl, optionally substituted at any one position of the phenyl group with chloride, bromide, iodide, cyano, or alkyl of 1 to 4 carbon atoms.

26. The medium of claim 25, wherein said oxidized form of said anodic compound is capable of absorbing in the NIR portion of the electromagnetic spectrum.

27. The medium of claim 25, wherein said medium further comprises a solvent and where said anodic compound is in solution in said solvent and interspersed in said polymer matrix.

28. The medium of claim 27, wherein said medium is self-erasing.

29. The medium of claim 25, wherein the outer product of the SOMO and HDOMO of said anodic compound results in a long axis transition dipole moment.

30. The medium of claim 29, wherein, said oxidized form of said anodic compound is capable of absorbing in the NIR portion of the electromagnetic spectrum and where said electrochromic medium further comprises a solvent and a cathodic electrochromic material.

31. The medium of claim 30, wherein said anodic compound is in solution in said solvent and interspersed in said polymer matrix.

32. The medium of claim 30, wherein said medium is solution-phase.

33. An electrochromic device, which comprises, as the medium of reversibly variable transmittance to light, the electrochromic medium of claim 30.

34. An electrochromic device, which comprises, as the medium of reversibly variable transmittance to light, the electrochromic medium of claim 31.

35. The device of claim 34, wherein said electrochromic medium is held in a space defined by two planar, parallel, spaced-apart walls, and a periphery defined by a seal, where the side of each of said walls that is in contact with said medium is coated with an electrode layer of electrically conductive material, and where said polymer matrix comprises less than about fifty percent by weight of said electrochromic medium.

36. An electrochromic window comprising an electrochromic medium, said electrochromic medium comprising a crosslinked polymer matrix and an anodic compound, wherein said window is capable of absorbing in the NIR portion of the electromagnetic spectrum, and said anodic compound has a redox potential greater than about 90 mV, and an absorption band having a λ

_max greater than approximately 750 nm, excluding therefrom the compounds of the formula;

wherein R₅₁ and R₅₄ are the same or different and are each selected from hydrogen and dialkylamino, wherein the alkyl groups are the same or different and are each of 1 to 6 carbon atoms;

R₅₂ is oxygen, sulfur or NR₅₅, wherein R₅₅ is the same as or different from R₅₃ and both R₅₅ and R₅₃ are selected from hydrogen, alkyl of 1 to 10 carbon atoms, phenyl optionally substituted at any one position with chloride, bromide, iodide, cyano, or alkyl of 1 to 4 carbon atoms, or benzyl, optionally substituted at any one position of the phenyl group with chloride, bromide, iodide, cyano, or alkyl of 1 to 4 carbon atoms.

37. The window of claim 36, wherein said electrochromic medium further comprises at least one solution-phase anodic compound where an oxidized form of said anodic compound has an E_SOMO−

E_HDOMO of less than 3.6 eV.

38. The window of claim 37, wherein the outer product of the SOMO and HDOMO of said anodic compound results in a long axis transition dipole moment.

39. The window of claim 37, wherein said electrochromic medium is held in a space defined by two planar, parallel, spaced-apart walls, and a periphery defined by a seal, where the side of each said walls that is in contact with said medium is coated with an electrode layer of electrically conductive material.