Coupled electrochromic compounds with photostable dication oxidation states

• US 6,249,369 B1
• Filed: 07/09/1999
• Issued: 06/19/2001
• Est. Priority Date: 07/09/1999
• Status: Expired due to Term

• Current Assignee: Gentex Corporation
• Original Assignee: Gentex Corporation
• Inventors: Guarr, Thomas F., Theiste, David A., Giri, Punam, Baumann, Kelvin L.
• Primary Examiner(s): Dang, Hung Xuan
• Application Number:
  US09/350,879
• Time in Patent Office: 711 Days
• Field of Search: 359/265, 359/273, 359/603, 359/604, 359/605, 359/272, 359/266, 359/267
• US Class Current: 359/265
• 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 2001/1502 complementary cell
• CPC Class Codes: G02F 2001/15145 the electrochromic layer comprises a mixture of anodic and cathodic compounds

Abstract

Coupling of anodic electrochromic compounds by a covalent bond or a bridge link which provides for electronic communication between the coupled electrochromic compounds results in coupled electrochromic compounds which exhibit greater stability as well as electrochromic activity that differs from the monomeric electrochromic compounds. Extension of the absorption spectrum into the near-infrared region of the spectrum is frequently observed. The coupled electrochromic compounds are highly suitable for use in electrochromic media used to produce electrochromic devices.

Claims

1. An electrochromic medium comprising two or more electroactive compounds, at least one of said electroactive compounds being a coupled electrochromic compound comprising a first anodic monomeric electrochromic compound coupled by a bridge comprising a covalent bond or an intervening hydrocarbon structure optionally containing one or more heteroatoms, to a second anodic monomeric electrochromic compound, and optionally additional monomeric electrochromic compounds such that electronic communication is exhibited between said anodic monomeric compounds.

2. The electrochromic medium of claim 1, wherein said first anodic monomeric electrochromic compound and said second anodic monomeric electrochromic compound are independently selected from the group consisting of substituted or unsubstituted dihydrophenazines, benzidines, phenothiazines, phenoxazines, triphenodioxazines, triphenodithiazines, quinoxalinophenazines, phenylenediamines, benzimidazole azines, benzoxazole azines, carbazoles, benzothiazoles, and mixtures thereof.

3. The electrochromic medium of claim 1 wherein said first anodic monomeric electrochromic compound and said second anodic monomeric electrochromic compound are optionally substituted 5,10-dihydrophenazines.

4. The electrochromic medium of claim 1 wherein the said coupled electrochromic compound is selected from one of the following structures:

where Y₁ and Y₂ are selected from O, S, and N—

R₇; and

X represents a coupling group or unit such as C_1-3 alkyl, C_2-6 alkenyl, C_2-6 alkynyl, C_4-10 cycloalkenyl, C_6-20 aryl, C_7-20 alkaryl, C_7-20 aralkyl;

optionally containing heteroatoms; and

R₁ through R₇ are the same or different hydrocarbon groups such as C_1-20 alkyl, C_2-20 alkenyl, C_2-20 alkynyl, C_3-20 cycloalkyl, C_4-20 cycloalkenyl, C_6-20 aryl, C_7-20 alkaryl, C_7-20 aralkyl; and

the like

n is an integer from 1-3; and

m is an integer from 1-4.

5. An electrochromic device which comprises an electrochromic medium of claim 1.

6. An electrochromic medium comprising two or more electroactive compounds, at least one of said electroactive compounds being a coupled electrochromic compound comprising a first anodic monomeric electrochromic compound coupled by a bridge comprising a covalent bond or an intervening hydrocarbon structure optionally containing one or more heteroatoms to a second anodic monomeric electrochromic compound, and optionally additional anodic monomeric compounds such that the absorption spectrum of said coupled electrochromic compound is different from the sum of the absorption spectrum of a mixture of the individual anodic monomeric compounds on an identical mole basis.

7. The medium of claim 6 wherein said first anodic monomeric electrochromic compound and said second anodic monomeric electrochromic compound are independently selected from the group consisting of substituted or unsubstituted dihydrophenazines, benzidines, phenothiazines, triphenodioxazines, phenoxazines, triphenodithiazines, quinoxalinophenazines, phenylenediamines, benzimidazole azines, benzoxazole azines, carbazoles, benzothiazoles azines, and mixtures thereof.

8. The medium of claim 6 herein the said coupled compound is selected from the group consisting of:

where Y₁ and Y₂ are selected from O, S, and N—

R₇; and

X represents a coupling group or unit such as C_1-3 alkyl, C_2-6 alkenyl, C_2-6 alkynyl, C_4-10 cycloalkenyl, C_6-20 aryl, C_7-20 alkaryl, C_7-20 aralkyl;

optionally containing heteroatoms; and

R₁ through R₇ are the same or different hydrocarbon groups such as C_1-20 alkyl, C_2-20 alkenyl, C_2-20 alkynyl, C_3-20 cycloalkyl, C_4-20 cycloalkenyl, C_6-20 aryl, C_7-20 alkaryl, C_7-20 aralkyl; and

the like

n is an integer from 1-3; and

m is an integer from 1-4.

9. The medium of claim 6 wherein said first anodic monomeric electrochromic compound and said second anodic monomeric electrochromic compound are optionally substituted 5,10-dihydrophenazines.

10. An electrochromic medium comprising two or more electroactive compounds, at least one of said electroactive compounds being a coupled electrochromic compound comprising a first anodic monomeric electrochromic compound coupled by a bridge comprising a covalent bond or an intervening hydrocarbon structure optionally containing one or more heteroatoms to a second anodic monomeric electrochromic compound such, and optionally additional anodic monomeric electrochromic compounds that the voltammogram of said coupled electrochromic compound is measurably different from said anodic monomeric compounds when run in the same solvent.

11. The medium of claim 10 wherein said first anodic monomeric electrochromic compound and said second anodic monomeric electrochromic compound are independently selected from the group consisting of substituted or unsubstituted dihydrophenazines, benzidines, phenothiazines, triphenodioxazines, phenoxazine, triphenodithiazines, quinoxalinophenazines, phenylenediamines, benzimidazole azines, benzoxazole azines, carbazoles, benzothiazole azines, and mixtures thereof.

12. The electrochromic device of claim 11 wherein said device is an electrochromic window.

13. The medium of claim 10 wherein said first anodic monomeric electrochromic compound and said second anodic monomeric electrochromic compound are optionally substituted 5,10-dihydrophenazines.

14. The medium of claim 10 wherein the coupled electrochromic compound is selected from the group consisting of:

where Y₁ and Y₂ are selected from O, S, and N—

R₇; and

X represents a coupling group or unit such as C_1-3 alkyl, C_2-6 alkenyl, C_2-6 alkynyl, C_4-10 cycloalkenyl, C_6-20 aryl, C_7-20 alkaryl, C_7-20 aralkyl;

optionally containing heteroatoms; and

R₁ through R₇ are the same or different hydrocarbon groups such as C_1-20 alkyl, C_2-20 alkenyl, C_2-20 alkynyl, C_3-20 cycloalkyl, C_4-20 cycloalkenyl, C_6-20 aryl, C_7-20 alkaryl, C_7-20 aralkyl; and

the like

n is an integer from 1-3; and

m is an integer from 1-4.

15. An electrochromic device comprising:

a first transparent substrate, a second substrate, a sealing member disposed between said first and second substrates to define a chamber;

an electrochromic medium disposed in said chamber, said electrochromic medium comprising two or more electroactive compounds, at least one of said electroactive compounds being a coupled electrochromic compound comprising a first anodic monomeric electrochromic compound coupled by a bridge to a second anodic monomeric electrochromic compound, such that electronic communication is exhibited between said first anodic compound and said second anodic compound.

16. An electrochromic device comprising:

a first transparent substrate, a second substrate, a sealing member disposed between said first and second substrates to define a chamber;

an electrochromic medium disposed in said chamber, said electrochromic medium comprising two or more electroactive compounds, at least one of said electroactive compounds being a coupled electrochromic compound comprising a first anodic monomeric electrochromic compound coupled by a bridge to a second anodic monomeric electrochromic compound, such that the absorption spectrum of said coupled electrochromic compound is different from the sum of the absorption spectrum of a mixture of the individual first and second anodic electrochromic compound on an identical mole basis.

17. An electrochromic device comprising:

a first transparent substrate, a second substrate, a sealing member disposed between said first and second substrates to define a chamber;

an electrochromic medium disposed in said chamber, said electrochromic medium comprising, two or more electroactive compounds, at least one of said electroactive compounds being a coupled electrochromic compound comprising a first anodic monomeric electrochromic compound coupled by a bridge to a second anodic monomeric electrochromic compound, such that the voltammogram of said coupled electrochromic compound is measurably different from said first and second monomeric electrochromic compounds when run in the same solvent.

18. A coupled electrochromic compound comprising a first anodic monomeric electrochromic compound coupled by a bridge to a second anodic monomeric electrochromic compound such that the absorption spectrum of said coupled electrochromic compound at the same relative electron density change as the monomeric compounds has at least one absorption band that is absent in the monomeric electrochromic compounds.

19. A coupled electrochromic compound comprising a first anodic monomeric electrochromic compound coupled by a bridge comprising a covalent bond or an intervening hydrocarbon structure optionally containing one or more heteroatoms to a second anodic monomeric electrochromic compound such that the absorption spectrum of said coupled electrochromic compound at the same relative electron density change as the monomeric compounds exhibits electrochromic activity at least one wavelength different from the monomeric compounds.

20. A compound of claim 19 wherein the said wavelength is in the near-infrared portion of the electromagnetic spectrum.