Electrochromic system

• US 6,183,878 B1
• Filed: 05/25/1999
• Issued: 02/06/2001
• Est. Priority Date: 08/06/1996
• Status: Expired due to Fees

• Current Assignee: Bayer AG
• Original Assignee: Bayer AG
• Inventors: Schaller, Jochen, Haarer, Dietrich, Claussen, Uwe, Berneth, Horst, Simmerer, Jürgen
• Primary Examiner(s): Lorin, Francis J.
• Application Number:
  US09/147,615
• Time in Patent Office: 623 Days
• Field of Search: 428/426, 428/583, 359/265, 252/301.35
• US Class Current: 428/583
• 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
• 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 428/12271 having discrete fastener, marginal fastening, taper, or end structure

Abstract

The invention concerns an electrochrome system comprising a mixture of reducible and oxidizable substances RED₁ and OX₂, at lest one RED₁′-OX₂′ pair being covalently interlinked via a bridge and, for at least one RED₁″ or OX₂″ substance, the reciprocal conversion of the oxidized form and the reduced form being brought about by the fracture or formation of a σ-bond. The electrochrome system is characterized by simplified electron transfer and reduced secondary reactions.

Claims

1. An electrochromic system comprising oxidizable substances RED₁ which, by releasing electrons at an anode, are converted from a weakly colored or colorless form into a colored form OX₁, and reducible substances OX₂ which, by accepting electrons at a cathode, are converted from a weakly colored or colorless form into a colored form RED₂, the absorbance in the visible region of the spectrum increasing in each of these cases, and the weakly colored or colorless form being recovered in each case after charge equalization, wherein the substances RED₁ and OX₂ are a mixture comprising at least one couple RED₁′

/OX₂′

which is linked covalently to one another via a bridge and at least one substance RED₁″

or OX₂″

in which the reciprocal conversion of oxidized and reducible form takes place by a σ

bond being broken or formed.

2. The electrochromic system as claimed in claim 1, which comprises at least one couple RED₁′

/OX₂′

corresponding to the formula (I)

3. The electrochromic system as claimed in claim 1, wherein the couple RED₁′

/OX₂′

is at least one electrochromic substance of the formulae

4. The electrochromic system as claimed in claim 1, wherein the couple RED₁′

/OX₂′

is a substance of the formulae (Ia) to (Id),

in which

OX₂′

represents the radical of a cathodically reducible substance which in a cyclic voltammogram, recorded in an inert solvent at room temperature, exhibits at least two chemically reversible reduction waves, the first of these reduction waves leading to an increase in the absorbance at at least one wavelength in the visible range of the electromagnetic spectrum,

RED₁′

represents the radical of the anodically reversibly oxidizable substance which in a cyclic voltammogram, recorded in an inert solvent at room temperature, exhibits at least two chemically reversible oxidation waves, the first of these oxidation waves leading to an increase in the absorbance at at least one wavelength in the visible range of the electromagnetic spectrum, and

B represents a bridge member.

5. The electrochromic system as claimed in claim 1, wherein the substance OX₂″

is a compound selected from the group consisting of the tetrazolium salts, benzo- or naphthotriazolium salts, cyclopropanes and [1.1.0]bicyclobutanes.

6. The electrochromic system as claimed in claim 1, wherein the substance OX₂″

is a tetrazolium salt, naphthotriazolium salt, cyclopropane and/or [1.1.0]bicyclobutane of the formulae

in which

R¹⁰¹ to R¹⁰⁵, independently of one another, represent C₆- to C₁₀-aryl or an aromatic or quasi-aromatic five- or six-membered heterocyclic ring, each of which is optionally benzanellated,

R¹⁰⁷, R¹⁰⁹, R¹¹³ and R¹¹⁴, independently of one another, represent a radical of the formulae (CV) to (CVII)

R¹⁰⁸, R¹¹⁵ and R¹¹⁶, independently of one another, represent C₆- to C₁₀-aryl, or a radical of the formulae (CV) to (CVII),

R¹¹⁰ to R¹¹², R¹¹⁷ and R¹¹⁸, independently of one another, represent hydrogen, C₁- to C₄-alkyl, halogeno or cyano,

E¹⁰¹ and E¹⁰², independently of one another, represent O, S or N—

R¹¹⁹,

R¹¹⁹ R¹²², independently of one another, represent C₁- to C₁₈-alkyl, C₂- to C₈-alkenyl, or C₄- to C₇-cycloalkyl, C₇- to C₁₅-aralkyl or C₆- to C₁₀-aryl,

R¹⁰⁶, R¹²⁰, R¹²¹, R¹²³ and R¹²⁴, independently of one another, represent hydrogen, C₁- to C₄-alkyl, C₁- to C₄-alkoxy, halogeno, cyano, nitro or C₁- to C₄-alkoxycarbonyl, or

R¹²⁰ and R¹²¹, or R¹²³ and R¹²⁴, jointly form a —

CH═

CH—

CH═

CH—

bridge,

and

X⁻

represents a colorless anion which is redox-inert under the conditions.

7. The electrochromic system as claimed in claim 1, which comprises as the couple RED₁′

/OX₂′

at least one substance of the formula (Ia)-(Id),

in which

OX₂′

represents a radical of the formulae (II), (III), (IV) or (V),

in which

R², R³, R⁴, R⁵, R⁸ and R⁹, independently of one another, represent C₁- to C₁₂-alkyl, C₂- to C₈-alkenyl, C₅- to C₇-cycloalkyl, C₇- to C₁₅-aralkyl or C₆- to C₁₀-aryl,

R⁶ and R⁷, independently of one another, represent hydrogen, methyl, ethyl, methoxy, ethoxy, fluoro, chloro, bromo, cyano, nitro, methoxycarbonyl or ethoxycarbonyl,

R¹⁰, R¹¹;

R¹², R¹³ and R¹⁴, R¹⁵, independently of one another, represent hydrogen or, if Z¹ represents a direct bond, in each case jointly represent a —

(CH₂)₂—

, —

(CH₂)₃—

or —

CH═

CH—

bridge,

or

R⁴, R⁵ and R⁸, R⁹, independently of one another, pairwise jointly represent a —

(CH₂)₂—

or —

(CH₂)₃—

bridge, if Z¹ represents a direct bond,

R⁶⁹ to R⁷⁴, independently of one another, represent hydrogen or C₁- to C₄-alkyl,

E¹ and E² are identical and represent O, S, NR¹ or C(CH₃)₂ or jointly form an —

N—

(CH₂)₂—

N—

bridge,

R¹ represents C₁- to C₁₂-alkyl, C₂- to C₄-alkenyl, C₅- to C₇-cycloalkyl, C₇- to C₁₅-aralkyl or C₆- to C₁₀-aryl,

Z¹ represents a direct bond, —

CH═

CH—

, —

C(CH₃)═

CH—

, —

C(CN)═

CH—

, —

C≡

C—

or —

CH═

N—

N═

CH—

,

Z² represents —

(CH₂)_r—

or —

CH₂—

C₆H₄—

CH₂—

,

r represents an integer between 1 and 6,

X⁻

represents a colorless anion which is redox-inert under the conditions,

the bond to the bridge member B being effected via one of the radicals R^2-R11 or, in the case where E¹ or E² represents NR¹, being effected via R¹ and the said radicals then representing a direct bond,

RED₁′

represents a radical of the formulae (X), (XI), (XII), (XIII), (XVI), (XVII), (XVIII) or (XX),

in which

R²⁸, R²⁹ to R³¹, R³⁴, R³⁵, R³⁸, R³⁹, R⁴⁶, R⁵³ and R⁵⁴, independently of one another, represent C₁- to C₁₂-alkyl, C₂- to C₈-alkenyl, C₅- to C₇-cycloalkyl, C₇- to C₁₅-aralkyl or C₆- to C₁₀-aryl,

R³², R³³, R³⁶, R³⁷, R⁴⁰, R⁴¹, R⁴⁷, R⁴⁸, R⁴⁹, R⁵⁰ to R⁵² R⁵⁵ and R⁵⁶, independently of one another, represent hydrogen, methyl, ethyl, methoxy, ethoxy, fluoro, chloro, bromo, cyano, nitro, methoxycarbonyl, ethoxycarbonyl or phenyl,

Z³ represents a direct bond, a —

CH═

CH—

or —

N═

N—

bridge,

═

Z⁴═

represents a direct double bond, a ═

CH—

CH═

or ═

N—

N═

bridge,

E³ to E⁵, E¹⁰ and E¹¹, independently of one another, represent O, S, NR⁵⁹ or C(CH₃)₂, but E³ and E⁴ have identical meanings,

E⁶ to E⁹, are identical to each other and represent S, Se or NR⁵⁹ or

E⁶ represents NR⁵⁹, where R⁵⁹ is a direct bond to the bridge B and

E⁷ to E⁹ have the abovementioned meanings, but need not be identical to one another,

R⁵⁹ represents C₁- to C₁₂-alkyl, C₂- to C₈-alkenyl, C₅- to C₇-cycloalkyl,, C₇- to C₁₅-aralkyl or C₆- to C₁₀-aryl,

R⁶¹, R⁶² and R⁶⁷, R⁶⁸, independently of one another, represent hydrogen, C₁- to C₄-alkyl, methoxycarbonyl, ethoxycarbonyl or phenyl or, pairwise jointly, represent a —

(CH₂)₃—

or —

(C₂)₄—

bridge,

R⁶³ to R⁶⁶ represent hydrogen and

v represents an integer from 1 to 6,

the bond to the bridge member B being effected by one of the radicals R^28-R41, R⁴⁶-R⁵⁶, R⁶¹, R⁶², R⁶⁷, R⁶⁸ or, in the case where one of the radicals E³-E¹¹ represents NR⁵⁹, being effected via R⁵⁹ and the said radicals then representing a direct bond,

B represents a bridge member of the formulae —

(CH₂)_n—

, —

(CH₂)_m—

O—

(CH₂)_p—

, —

(CH)_m—

NR⁶⁰—

(CH₂)_p—

, —

(CH₂)_m—

C₆H₄—

(CH₂)_p—

, —

[O—

(CH₂)_p]_o—

O—

, —

[NR⁶⁰—

(CH₂)_p]_o—

NR⁶⁰—

, —

[C₆H₄—

(CH₂)_p]_o—

C₆H₄—

, —

(CH₂)_m—

OCO—

C₆H₄—

COO—

(CH₂)_p—

, —

(CH₂)_m—

NHCO—

C₆H₄—

CONH—

(CH₂)_p—

, —

(CH₂)_m—

NHCONH—

C₆H₄—

NHCONH—

(CH₂)_p—

, —

(CH₂)_m—

OCO—

(CH₂)_t—

COO—

(CH₂)—

, —

(CH₂)_m—

NHCO—

(CH₂)_t—

CONH—

(CH)_p—

, —

(CH₂)_m—

NHCONH—

(CH₂)_t—

NHCONH—

(CH₂)_p—

,

R⁶⁰ represents methyl, ethyl, benzyl or phenyl,

n represents an integer from 1 to 10,

m and p, independently of one another, represent an integer from 0 to 4,

o represents an integer from 0 to 2 and

t represents an integer from 1 to 6 and

as the substance OX₂″

comprises at least one tetrazolium salt of the formula (CI),

in which

R¹⁰¹ and R¹⁰² correspond to a radical of formula (CXIX),

R¹⁰³ corresponds to a radical of formula (CXX),

R¹⁵⁷, ¹⁵⁹ and R¹⁶⁰, independently of one another, represent hydrogen, methyl, ethyl, methoxy, ethoxy, cyano, nitro, —

N⁺(CH₃)₃ or COOH, or

R¹⁵⁷ and R¹⁵⁹ jointly form an —

O—

CH₂—

O—

bridge,

R¹⁵⁸ represents hydrogen, methyl, methoxy or chloro,

R¹⁶¹ represents methyl, difluoromethyl, trifluoromethyl, methoxycarbonyl, ethoxycarbonyl or phenyl,

R¹⁶² represents hydrogen, methyl, ethyl, phenyl or chloro, or

R¹⁶¹ and R¹⁶² jointly form a —

CH═

CH—

CH═

CH—

or —

CH═

CH—

C(OCH₃)═

CH—

bridge,

E¹¹² represents S,

X⁻

represents a colorless anion which is redox-inert under the conditions.

8. The electrochromic system as claimed in claim 1, which comprises as the couple RED₁′

/OX₂′

, at least one substance of the formula (Ia)-(Id)

in which

OX₂′

represents a radical of the formulae (II), (IV) or (V) as claimed in claim 7,

in which

R², R⁴ and R⁸ represent a direct bond to the bridge member B,

R³, R⁵ and R⁹, independently of one another, represent methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, benzyl or phenyl or, in the case of the formulae Ic or Id likewise represent a direct bond to the bridge member B,

R⁶ and R⁷ are identical and represent hydrogen, methyl, methoxy, chloro, cyano or methoxycarbonyl,

R¹⁰, R¹¹;

R¹², R¹³ and R¹⁴, R¹⁵, independently of one another, represent hydrogen or, if Z¹ represents a direct bond, in each case pairwise jointly represent a —

CH═

CH—

bridge,

R⁶⁹ to R⁷² are identical and represent hydrogen, methyl or ethyl,

R⁷³ and R⁷⁴ represent hydrogen,

E¹ and E² are identical and represent O or S,

Z¹ represents a direct bond or —

CH═

CH—

,

X¹ represents a colorless anion which is redox-inert under the conditions,

RED₁′

represents a radical of the formulae (X), (XII), (XIII), (XVI) or (XVII) as claimed in claim 7,

in which

R²⁸, R³⁴, R³⁸, R⁴⁶ and R⁴⁹ represent a direct bond to the bridge member B,

R²⁹ to R³¹, R³⁵ and R³⁹, independently of one another, represent methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, benzyl or phenyl or, in the case of the formulae Ib or Id, R³⁰, R³⁵ and R³⁹ likewise represent the direct bond to the bridge member B,

R³², R⁴⁷ and R⁴⁸ represent hydrogen,

R³⁶, R³⁷, R⁴⁰, R⁴¹ and R⁵⁰ to R⁵², independently of one another, represent hydrogen, methyl, methoxy, chloro, cyano, methoxycarbonyl or phenyl or, in the case of the formula Ib or Id, R⁵¹ likewise represents a direct bond to the bridge member B,

Z³ represents a direct bond, a —

CH═

CH—

or —

N═

N—

bridge,

═

Z⁴═

represents a direct double bond, a ═

CH—

CH═

or ═

N—

N═

bridge,

E³ to E⁵ independently of one another, represent O, S or NR⁵⁹, but E³ and E⁴ have identical meanings,

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

R⁵⁹ represents methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, benzyl or phenyl or, in the case of the formula XVI in Ib or Id likewise represents a direct bond to the bridge member B,

B represents a bridge member of the formulae —

(CH₂)_n—

;

—

(CH₂)_m—

O—

(CH₂)_p—

, —

(CH₂)_m—

NR⁶⁰—

(CH₂)_p—

, —

(CH₂)_m—

C₆H₄—

(CH₂)_p—

, —

O—

(CH₂)_p—

O—

, —

NR⁶⁰—

(CH₂)_po-NR⁶⁰—

, —

(CH₂)_m—

OCO—

C₆H₄—

COO—

(CH₂)_p—

,

—

(CH₂)_m—

NHCO—

C₆H₄—

CONH—

(CH₂)_p—

, —

(CH₂)_m—

NHCONH—

C₆H₄—

NHCONH—

(CH₂)_p—

, —

(CH₂)_m—

OCO—

(CH)_t—

COO—

(CH₂)_p—

, —

(CH₂)_m—

NHCO—

(CH₂)_t—

CONH—

(CH₂)_p—

, —

(CH₂)_m—

NHCONH—

(CH₂)_t—

NHCONH—

(CH₂)_p—

,

R⁶⁰ represents methyl,

n represents an integer from 1 to 10,

m and p are identical and represent an integer from 0 to 2 and

t represents an integer from 1 to 6 and,

as the substance OX₂″

comprises at least one substance of the formula (CI),

in which

R¹⁰¹, R¹⁰², R¹⁰³ and X⁻

have the meanings specified in claim 6.

9. Electrochromic system as claimed in claim 1, which comprises, as the couple RED₁′

/X₂′

, at least one substance of the formula (Ia) corresponding to one of the formulae

or at least one substance of the formula (Ib) corresponding to one of the formulae

or at least one substance of the formula (Ic) corresponding to one of the formulae

in which

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

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

R¹² and R¹³ represent hydrogen or, if Z¹ represents a direct bond, jointly 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 to E⁵, independently of one another, represent O, S, or NR⁵⁹, E³ and E⁴ being identical, however,

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

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, but are preferably identical,

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 a colorless anion which is redox-inert under the conditions,

where the representation

in the above-specified formulae represents a link in the o-, m-, or p- position, and

b) comprises, as the substance OX₂″

, at least one substance of the formula (CI) as claimed in claim 6.

10. An electrochromic fluid comprising an electrochromic system as claimed in at least one of claim 1 and at least one inert solvent.

11. An electrochromic device containing an electrochromic fluid as claimed in claim 10.

12. The electrochromic device as claimed in claim 11, which is designed as a cell such as e.g. a solar cell, as a window pane, mirror, canopy or display.

13. The electrochromic device as claimed in claim 11, which comprises two transparent glass or plastic panes which face one another, one of them optionally being mirrored and whose sides which face one another are coated electroconductively, between which the electrochromic fluid is contained.

14. The electrochromic device as claimed in claim 12, which comprises two transparent glass or plastic panes which face one another, one of them optionally being mirrored and whose sides which face one another are coated electroconductively, between which the electrochromic fluid is contained.