Electrochromic device and novel electrochromic compounds

• US 6,806,989 B2
• Filed: 10/23/2002
• Issued: 10/19/2004
• Est. Priority Date: 10/26/2001
• Status: Expired due to Fees

• Current Assignee: Bayer AG
• Original Assignee: Bayer AG
• Inventors: Berneth, Horst
• Primary Examiner(s): Epps, Georgia
• Assistant Examiner(s): CHOI, WILLIAM C
• Application Number:
  US10/278,309
• Publication Number:
  US 20030129368A1
• Time in Patent Office: 727 Days
• Field of Search: 359/265, 359/267, 359/268, 359/272, 359/275, 252/582, 252/583, 252/600, 544/347, 546/257, 204/290.07, 428/426, 428/427, 428/583
• 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: Y10T 428/24802 Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]

Abstract

Asymmetrical compounds composed of two different heterocyclic and/or carbocyclic rings linked via a conjugated chain containing an uneven number of chain atoms are useful electrochromic compounds and can be used for producing electrochromic devices.

Claims

1. An electrochromic device comprising:

(a) a pair of glass plates or a pair of plastic plates or a pair of plastic films, wherein (A) both plates or both films are transparent and at least one plate has a side with a transparent electrically conductive coating that is optionally divisible into separate, individually contacted area segments or (B) (i) one plate or one film is transparent, (ii) the other plate or film is mirrored and (iii) at least one plate or at least one film has a transparent, electrically conductive coating that is optionally divisible into separate, individually contacted area segments and,

(b) a sealing ring for joining together the plates or the films on the sides having an conductive coating, wherein the two plates or films and the sealing ring form a volume, and

(c) an electrochromic medium for filling the volume, wherein the electrochromic medium includes at least one oxidizable electrochromic substance RED₁ and at least one reducible electrochromic substance OX₂, wherein the substance RED₁ is an electrochromic compound of the formula (CC);

wherein

A is an aromatic or a quasi-aromatic, heterocyclic 5- or 6-membered ring in which X²⁰¹ is located in the 2- or 4-position relative to the point of attachment,

B is an aromatic or a quasi-aromatic, carbocyclic or heterocyclic 5- or 6-membered ring in which Y²⁰¹ is located in the 2- or 4-position relative to the point of attachment,

X²⁰¹ is NR²⁰¹, O or S,

Y²⁰¹ is NR²⁰²R²⁰³, OR²⁰⁴ or SR²⁰⁵,

Z²⁰¹ to Z²⁰³, independently of one another, are carbon or nitrogen,

R²⁰¹ to R²⁰⁵, independently of one another, are alkyl, alkenyl, cycloalkyl, aralkyl or aryl, and

R²⁰² to R²⁰⁵ may additionally be hydrogen,

is an integer from 0 to 3, and

Z²⁰¹ to Z²⁰³ may form a bridge with one another or with the rings A and/or B,

and/or the substance OX₂ used is an electrochromic compound of the formula (CCl)

wherein

C is an aromatic or a quasi-aromatic, heterocyclic 5- or 6-membered ring in which X²⁰² is located in the 2- or 4-position relative to the point of attachment,

D is an aromatic or a quasi-aromatic, carbocyclic or heterocyclic 5- or 6-membered ring in which Y²⁰² is located in the 2- or 4-position relative to the point of attachment, or

is ═

C(CN)₂, ═

C(CN)COOalkyl or ═

C(COOalkyl)₂,

X²⁰² is N⁺R²⁰⁶, O⁺ or S⁺,

Y²⁰² is NR²⁰⁷, O, S, N—

CN or C(CN)₂,

Z²⁰⁴ to Z²⁰⁶, independently of one another, are carbon or nitrogen,

R²⁰⁶ and R²⁰⁷, independently of one another, are alkyl, alkenyl, cycloalkyl, aralkyl or aryl,

j is an integer from 0 to 3, and

Z²⁰⁴ to Z²⁰⁶ may form a bridge with one another or with the rings C and/or D,

wherein the rings A, B, C and D may carry further substituents.

2. The electrochromic device according to claim 1, wherein

A is an optionally benzo-fused pyrroline, pyrazoline, imida zoline, triazoline, oxazoline, thiazoline, oxadiazoline, thiadiazoline, dithioline, dihydropyridine, dihydropyrimidine or dihydropyrazine ring,

B is an optionally benzo-fused cyclopentadiene or benzene ring,

X²⁰¹ is NR²⁰¹,

Y²⁰¹ is NR²⁰²R²⁰³, OR²⁰⁴ or SR²⁰⁵ and is located in the 2- or 4-position relative to the point of attachment,

Z²⁰¹ to Z²⁰³, independently of one another, are carbon or nitrogen,

R²⁰¹ to R²⁰⁵, independently of one another, are C₁- to C₁₂-alkyl, C₃- to C₇-cycloalkyl, C₇- to C₁₅-aralkyl or C₆- to C₁₀-aryl, and

R²⁰² to R²⁰⁵ may additionally be hydrogen,

i is 0 or 1, and

(Z²⁰²═ Z²⁰³)_i may be phenylene,

C is an optionally benzo-fused pyrrole, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, thiadiazole, dithiol, pyridine, pyrimidine or pyrazine ring,

D is an optionally benzo-fused cyclopentene or benzoquinoid ring, or

is ═

C(CN)₂,

X²⁰² is N⁺R²⁰⁶, O⁺ or S⁺,

Y²⁰² is NR²⁰⁷, O, S, N—

CN or C(CN)₂ and is located in the 2- or 4-position relative to the point of attachment,

Z²⁰⁴ to Z²⁰⁶, independently of one another, are carbon or nitrogen,

R²⁰⁶ and R²⁰⁷, independently of one another, are C₁- to C₁₂-alkyl, C₃- to C₇-cycloalkyl, C₇- to C₁₅-aralkyl or C₆- to C₁₀-aryl,

j is an integer from 0 to 3, and

(Z²⁰⁵═

Z²⁰⁶)_j may be phenylene.

3. The electrochromic device according to claim 1, wherein X²⁰¹ and Y²⁰¹ and X²⁰² and Y²⁰² are separated by no more than 8 atoms.

4. The electrochromic device according to claim 1, wherein

A is an indoline, benzimidazoline, benzoxazoline, benzthiazoline, 1,3-dithioline, dihydropyridine or dihydroquinoline radical,

B is an indene or benzene ring,

X²⁰¹ is NR²⁰¹ or S,

Y²⁰¹ is NR²⁰²R²⁰³ or OR²⁰⁴ and is located in the 2-position relative to the point of attachment when B is an indene ring, and is loacted in the 4-position relative to the point of attachment when B is a benzene ring,

Z²⁰¹—

(Z²⁰²═

Z²⁰³)_i is N, CH, CH—

N═

N, N—

N═

CH, CH—

CH═

CH or N—

N═

N,

R²⁰¹ to R²⁰⁴, independently of one another, are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, cyclohexyl, benzyl, phenethyl, phenylpropyl or phenyl,

C is a benzimidazole, benzoxazole, benzthiazole, 1,3-dithiol, pyridine or quinoline ring,

D is an indane or benzoquinoid ring,

X²⁰² is N⁺R²⁰⁶ or S⁺,

Y²⁰² is O, N—

CN or C(CN)₂,

Z²⁰⁴═

(Z²⁰⁵—

Z²⁰⁶)_j is N or CH, and

R²⁰⁶ is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, cyclohexyl, benzyl, phenethyl, phenylpropyl or phenyl.

5. The electrochromic device according to claim 1, wherein

A is a radical selected from the group consisting of the formulae

B is a radical selected from the group consisting of the formulae

Z²⁰¹—

(Z²⁰²═

Z²⁰³)_i is N, CH, or N—

N═

CH,

R²⁰¹ to R²⁰⁴ and R²¹³, independently of one another, are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, cyclohexyl, benzyl, phenethyl, phenylpropyl or phenyl,

R²¹⁰ and R²¹⁴, independently of one another, are hydrogen, methyl, ethyl, methoxy, ethoxy, chlorine, COOCH₃, COOC₂H₅, cyano or nitro,

R²¹¹ and R²¹², independently of one another, are hydrogen, methyl, ethyl, methoxy, ethoxy, methyltho, ethylthio, COOCH₃, COOC₂H₅ or cyano, or together are a —

CH═

CH—

CH═

CH—

bridge,

C is a radical selected from the group consisting of the formulae

D is a radical selected from the group consisting of the formulae

Z²⁰⁴═

(Z²⁰⁵—

Z²⁰⁶)_j is N or CH,

R²⁰⁶ is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, cyclohexyl, benzyl, phenethyl, phenylpropyl or phenyl,

R²²⁰ and R²²⁴, independently of one another, are hydrogen, methyl, ethyl, methoxy, ethoxy, chlorine, COOCH₃, COOC₂H₅, cyano or nitro, and

R²²¹ and R²²², independently of one another, are hydrogen, methyl, ethyl, methoxy, ethoxy, methylthio, ethylthio, COOCH₃, COOC₂H₅ or cyano or together are a —

CH═

CH—

CH═

CH—

bridge.

9. The device of claim 1, wherein the device is a window.

10. The device of claim 1, wherein the device is a screen.

11. The device of claim 1, wherein the device is a separating screen or a sight protection screen.

12. The device of claim 1, wherein the device is a glazing.

13. The device of claim 1, wherein the device is a roof glazing.

14. The device of claim 1, wherein the device is a light filter.

15. The device of claim 1, wherein the device is a mirror.

16. The device of claim 1, wherein the device is a display device.

6. An electrochromic compound of the formula (CC):

A is an aromatic or a quasi-aromatic, heterocyclic 5- or 6-membered ring in which X²⁰¹ is located in the 2- or 4-position relative to the point of attachment,

B is an aromatic or a quasi-aromatic, carbocyclic or \ heterocyclic 5- or 6-membered ring in which Y²⁰¹ is located in the 2- or 4-position relative to the point of attachment,

X²⁰¹ is NR²⁰¹, O or S,

Y²⁰¹ is NR²⁰²R²⁰³, OR²⁰⁴ or SR²⁰⁵,

Z²⁰¹ to Z²⁰³, independently of one another, are carbon or nitrogen,

R²⁰¹ to R²⁰⁵, independently of one another, are alkyl, alkenyl, cycloalkyl, aralkyl or aryl, and

R²⁰² to R²⁰⁵ may additionally be hydrogen,

i is an integer from 0 to 3, and

Z²⁰¹ to Z²⁰³ may form a bridge with one another or with the rings A and/or B,

wherein

A is not be a benzthiazoline radical when Z²⁰¹—

(Z²⁰²═

Z²⁰³)_i is N—

N═

CH or N and B is an N,N-disubstituted aniline radical,

A is not be a dithiazoline radical when Z²⁰¹—

(Z²⁰²═

Z²⁰³)_i is N and B is an N,N-disubstituted aniline radical,

Z²⁰¹—

(Z²⁰²═

Z²⁰³)_i is not be CH—

N═

N,

or of the formula (CCl)

wherein

C is an aromatic or a quasi-aromatic, heterocyclic 5- or 6-membered ring in which X²⁰² is located in the 2- or 4-position relative to the point of attachment,

D is an aromatic or a quasi-aromatic, carbocyclic or heterocyclic 5- or 6-membered ring in which Y²⁰² is located in the 2- or 4-position relative to the point of attachment, or

is ═

C(CN)₂, ═

C(CN)COOalkyl or ═

C(COOalkyl)₂,

X²⁰² is N⁺R²⁰⁶, O⁺ or S⁺,

Y²⁰² is NR²⁰⁷, O, S, N—

CN or C(CN)₂,

Z²⁰⁴ to Z²⁰⁶, independently of one another, are carbon or nitrogen,

R²⁰⁶ and R²⁰⁷, independently of one another, are alkyl, alkenyl, cycloalkyl, aralkyl or aryl,

j is an integer from 0 to 3, and

Z²⁰⁴ to Z²⁰⁶ may form a bridge with one another or with the rings C and/or D,

wherein

C is not be a pyridinium radical when Z⁴═

(Z⁵—

Z⁶)_j is CH and D is an indane-1,3-dion-2-ylidene radical.

7. An electrochromic compound of the formula (L)

8. An electrochromic medium comprising at least one electrochromic substance of the formulae (CC), (CCl) or (L), wherein formula (CC) is

wherein

A is an aromatic or a quasi-aromatic, heterocyclic 5- or 6-membered ring in which X²⁰¹ is located in the 2- or 4-position relative to the point of attachment,

B is an aromatic or a quasi-aromatic, carbocyclic or heterocyclic 5- or 6-membered ring in which Y²⁰¹ is located in the 2- or 4-position relative to the point of attachment,

X²⁰¹ is NR²⁰¹, O or S,

Y²⁰¹ is NR²⁰²R²⁰³, OR²⁰⁴ or SR²⁰⁵,

Z²⁰¹ to Z²⁰³, independently of one another, are carbon or nitrogen,

R²⁰¹ to R²⁰⁵, independently of one another, are alkyl, alkenyl, cycloalkyl, aralkyl or aryl, and

R²⁰² to R²⁰⁵ may additionally be hydrogen,

i is an integer from 0 to 3, and

Z²⁰¹ to Z²⁰³ may form a bridge with one another or with the rings A and/or B,

and/or the substance OX₂ used is an electrochromic compound of wherein the formula (CCl) is:

wherein

C is an aromatic or a quasi-aromatic, heterocyclic 5- or 6-membered ring in which X²⁰² is located in the 2- or 4-position relative to the point of attachment,

D is an aromatic or a quasi-aromatic, carbocyclic or heterocyclic 5- or 6-membered ring in which Y²⁰² is located in the 2- or 4-position relative to the point of attachment, or

is ═

C(CN)₂, ═

C(CN)COOalkyl or ═

C(COOalkyl)₂,

X²⁰² is N⁺R²⁰⁶, O⁺ or S⁺,

Y²⁰² is NR²⁰⁷, O, S, N—

CN or C(CN)₂,

Z²⁰⁴ to Z²⁰⁶, independently of one another, are carbon or nitrogen,

R²⁰⁶ and R²⁰⁷, independently of one another, are alkyl, alkenyl, cycloalkyl, aralkyl or aryl,

j is an integer from 0 to 3, and

Z²⁰⁴ to Z²⁰⁶ can form a bridge with one another or with the rings C and/or D,

wherein

C is not a pyridinium radical when Z⁴═

(Z⁵—

Z⁶)_j is CH and D is an indane-1,3-dion-2-ylidene radical, and

wherein formula (L) is