Electrochromic system with coupled RED-OX system and special anions

• US 6,767,481 B2
• Filed: 05/17/2002
• Issued: 07/27/2004
• Est. Priority Date: 08/18/1997
• Status: Expired due to Fees

• Current Assignee: Bayer AG
• Original Assignee: Bayer AG
• Inventors: Kostromine, Serguei, Berneth, Horst
• Primary Examiner(s): Tucker, Philip C.
• Application Number:
  US10/150,335
• Publication Number:
  US 20020197486A1
• Time in Patent Office: 802 Days
• Field of Search: 252/583, 252/586, 359/265, 359/267, 359/270, 359/272, 359/275
• US Class Current: 252/583
• CPC Class Codes: C09K 9/02 Organic tenebrescent materials
• CPC Class Codes: G02F 1/1516 comprising organic material
• 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
• CPC Class Codes: Y10T 428/31504 Composite [nonstructural laminate]

Abstract

This invention relates to electrochromic fluids based on electrochromic systems containing at least one oxidizable substance RED₁ and at least one reducible substance OX₂ linked covalently by a bridge that are suitable for use in electrochromic devices.

Claims

1. An electrochromic fluid comprising

(i) an electrochromic system comprising a weakly colored or colorless combination of at least one oxidizable substance RED₁ that releases electrons at an anode and in so doing undergoes transition into a substance OX₁ and at least one reducible substance OX₂ that accepts electrons at a cathode and in so doing undergoes transition into a substance RED₂, with the proviso that at least one of OX₁ or RED₂ is accompanied by an increase in the absorbance in the visible region of the spectrum and thereby becomes colored and the combination is restored to the weakly colored or colorless form after charge equalization, wherein

(1) at least one of the substances RED₁ is linked covalently to at least one of the substances OX₂ by a bridge, and

(2) at least one anion X⁻

having (a) a molar mass greater than 200 g/mol and/or (b) a cagelike structure is present, and

(ii) at least one inert solvent.

2. An electrochromic fluid according to claim 1 wherein the anion X⁻

is the counterion of the reducible substance OX₂ and/or a constituent of an inert conductive salt.

3. An electrochromic fluid according to claim 1 wherein the reducible substance OX₂ has no positive charge and the anion X⁻

is a constituent of an inert conductive salt.

4. An electrochromic fluid according to claim 1 wherein the anion X⁻

is C₁₀-C₂₅-alkanesulphonate;

C₅-C₁₈-perfluoroalkanesulphonate;

C₁₃-C₂₅-alkanoate;

benzenesulphonate substituted by nitro, C₄-C₂₅-alkyl, perfluoro-C₁-C₈-alkyl, C₁-C₁₂-alkoxycarbonyl, or dichloro;

naphthalenesulphonate or biphenylsulphonate, each of which is unsubstituted or substituted by nitro, cyano, hydroxyl, C₁-C₂₅-alkyl, C₁-C₁₂-alkoxy, amino, C₁-C₁₂-alkoxycarbonyl, or chloro;

benzenesulphonate, naphthalenesulphonate, or biphenyldisulphonate, each of which is unsubstituted or substituted by nitro, cyano, hydroxyl, C₁-C₂₅-alkyl, C₁-C₁₂-alkoxy, C₁-C₁₂-alkoxycarbonyl or chloro;

benzoate substituted by dinitro, C₆-C₂₅-alkyl, C₄-C₁₂-alkoxycarbonyl, benzoyl, chlorobenzoyl, or toluoyl;

the anion of naphthalenedicarboxylic acid;

diphenyl ether disulphonate;

tetraphenylborate;

cyanotriphenylborate, tetra-C₃-C₂₀-alkoxyborate;

tetraphenoxyborate;

7,8- or 7,9-dicarba-nido-undecaborate(1-) or (2-), each of which is unsubstituted or substituted on the B and/or C atoms by one or two C₁-C₁₂-alkyl or phenyl groups;

dodecahydrodicarbadodecaborate(2-);

or B—

C₁-C₁₂-alkyl-C-phenyl-dodecahydrodicarbadodecaborate(1-).

5. An electrochromic fluid according to claim 1 comprising at least one electrochromic substance of formula (I)

6. An electrochromic fluid according to claim 1 wherein in formula (I) Y represents OX₂ and Z represents RED₁ and Y and Z alternate in their sequence.

7. An electrochromic fluid according to claim 1 comprising at least one electrochromic substance of the formulas

8. An electrochromic fluid according to claim 1 comprising at least one electrochromic substance of the formulas

9. An electrochromic fluid according to claim 1 comprising at least one electrochromic substance of the formulas

10. An electrochromic fluid according to claim 1 comprising at least one electrochromic substance of the formulas

11. An electrochromic fluid according to claim 1 comprising at least one electrochromic substance of the formulas

12. An electrochromic system according to claim 1 comprises at least one electrochromic substance of the formulas

wherein

R³, R⁵, R³⁵ and R³⁹ independently of one another represent methyl, ethyl, propyl, butyl, pentyl, hexyl or benzyl,

R⁶ R⁷ and R³⁶ R³⁷ in pairs are identical and represent hydrogen, methyl, methoxy, chloro, cyano or methoxycarbonyl,

R¹² and R¹³ represent hydrogen or, if Z¹ denotes a direct bond, together represent a —

CH═

CH—

bridge,

R⁶⁹ to R⁷² are identical and represent hydrogen or methyl,

E¹ and E² are identical and represent O or S,

Z¹ represents a direct bond or —

CH═

CH—

,

R³², R⁴⁷ and R⁴⁸ represent hydrogen,

E³, E⁴, E⁵ independently of one another represent O, S or NR⁵⁹, with the proviso that E³ and E⁴ are identical,

R²⁹, R³¹, and R⁵⁹ independently of one another represent methyl, ethyl, propyl, butyl, pentyl, hexyl or benzyl,

R⁴⁰ and R⁴¹ are identical and represent hydrogen, methyl, ethyl, propyl, butyl or phenyl,

Z³ represents a direct bond, —

CH═

CH—

or —

N═

N—

,

R⁵⁰ to R⁵² independently of one another represent hydrogen, methyl, methoxy, chloro, cyano, methoxycarbonyl, ethoxycarbonyl or phenyl,

E⁶ to E⁹ are identical to one another and represent S, Se or NR⁵⁹,

Z⁴ represents a direct double bond, a ═

CH—

CH═

or ═

N—

N═

bridge,

m represents an integer from 1 to 5,

u represents 0 or 1 and

X⁻

represents C₁₅-C₂₀-alkanesulphonate, C₅-C₈-perfluoroalkane-sulphonate, mono- or dibutylbenzenesulphonate, mono- or di-tert-butylbenzenesulphonate, octylbenzenesulphonate, dodecylbenzenesulphonate, naphthalenesulphonate, biphenylsulphonate, nitrobenzenedisulphonate, naphthalenedisulphonate, dibutylnaphthalenesulphonate, biphenyldisulphonate, benzoylbenzoate, cyanotriphenylborate, tetra-C₃- to C₈-alkoxyborate, tetraphenoxyborate, 7,8-or 7,9-dicarba-nido-undecaborate(1-) or (2-) or dodecahydrodi-carbadodecaborate(2-), with the proviso that for polyvalent anions X⁻

represents one equivalent of this anion.

13. An electrochromic device containing an electrochromic fluid according to claim 1.

14. An electrochromic device according to claim 13 configured as a cell, a window pane, a mirror, a sunroof, or a display device.

15. An electrochromic device according to claim 13 comprising two facing transparent glass or plastic plates in which the facing sides carry an electro-conductive coating and between which is contained the electrochromic fluid.

16. An electrochromic device according to claim 15 wherein one of the plates is mirrored.