Coupled electrochromic compounds with photostable dication oxidation states

• US 6,560,004 B2
• Filed: 06/19/2001
• Issued: 05/06/2003
• 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:
  US09/884,717
• Publication Number:
  US 20020018281A1
• Time in Patent Office: 686 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 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 two or more electroactive compounds, at least one of the 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 the anodic monomeric compounds.

2. The electrochromic device according to claim 1, wherein the first anodic monomeric electrochromic compound and the 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 device according to claim 1, wherein the first anodic monomeric electrochromic compound and the second anodic monomeric electrochromic compound are optionally substituted 5,10-dihydrophenazines.

4. The electrochromic device according to claim 1, wherein the coupled electrochromic compound is selected from one of the following structures:

wherein Y₁ and Y₂ are the same or different and are selected from the group consisting of O, S, and N—

R₇;

wherein X is selected from the group consisting of a single bond, and a coupling group or unit consisting of C_1-3 alkyl, C_2-6 alkenyl, C_2-6 alkynyl, C_4-10 cycloalkenyl, C_6-20 aryl, C_7-20 alkaryl, or C_7-20 aralkyl, optionally containing heteroatoms;

wherein R₁-R₇ are the same or different and are selected from the group consisting of 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, and C_7-20 aralkyl;

wherein n is an integer from 1-3; and

wherein m is an integer from 1-4.

5. The electrochromic device according to claim 1, wherein said device is an electrochromic window.

6. 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 comprising two or more electroactive compounds, at least one of the 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 the 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 electrochromic device according to claim 6, wherein the first anodic monomeric electrochromic compound and the 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, benzothiazole azines, and mixtures thereof.

8. The electrochromic device according to claim 6, wherein the coupled electrochromic compound is selected from the group consisting of:

wherein Y₁ and Y₂ are the same or different and are selected from the group consisting of O, S, and N—

R₇;

wherein X is selected from the group consisting of a single bond, and a coupling group or unit consisting of C_1-3 alkyl, C_2-6 alkenyl, C_2-6 alkynyl, C_4-10 cycloalkenyl, C_6-20 aryl, C_7-20 alkaryl, or C_7-20 aralkyl, optionally containing heteroatoms;

wherein R₁-R₇ are the same or different and are selected from the group consisting of 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, and C_7-20 aralkyl;

wherein n is an integer from 1-3; and

wherein m is an integer from 1-4.

9. The electrochromic device according to claim 6, wherein the first anodic monomeric electrochromic compound and the second anodic monomeric electrochromic compound are optionally substituted 5,10-dihydrophenazines.

10. The electrochromic device according to claim 6, wherein said device is an electrochromic window.

11. 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 two or more electroactive compounds, at least one of the 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 electrochromic compounds, such that the voltammogram of the coupled electrochromic compound is measurably different from the anodic monomeric compounds when run in the same solvent.

12. The electrochromic device according to claim 11, wherein the first anodic monomeric electrochromic compound and the 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, benzothiazole azines, and mixtures thereof.

13. The electrochromic device according to claim 11, wherein the first anodic monomeric electrochromic compound and the second anodic monomeric electrochromic compound are optionally substituted 5,10-dihydrophenazines.

14. The electrochromic device according to claim 11, wherein the coupled electrochromic compound is selected from the group consisting of:

wherein Y₁ and Y₂ are the same or different and are selected from the group consisting of O, S, and N—

R₇;

wherein X is selected from the group consisting of a single bond, and a coupling group or unit consisting of C_1-3 alkyl, C_2-6 alkenyl, C_2-6 alkynyl, C_4-10 cycloalkenyl, C_6-20 aryl, C_7-20 alkaryl, or C_7-20 aralkyl, optionally containing heteroatoms;

wherein R₁-R₇ are the same or different and are selected from the group consisting of 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, and C_7-20 aralkyl;

wherein n is an integer from 1-3; and

wherein m is an integer from 1-4.

15. The electrochromic device according to claim 11, wherein said device is an electrochromic window.