EP1015524A1

EP1015524A1 - Electrochromic system with coupled red-ox system and special anions

Info

Publication number: EP1015524A1
Application number: EP98946284A
Authority: EP
Inventors: Horst Berneth; Serguei Kostromine
Original assignee: Bayer AG
Current assignee: Bayer Chemicals AG
Priority date: 1997-08-18
Filing date: 1998-08-06
Publication date: 2000-07-05
Also published as: US20020197486A1; DE19735733A1; WO1999009111A1; AU733812B2; US6417951B1; AU9339398A; CA2300131A1; JP2001515120A; US6767481B2; KR20010022994A

Abstract

The invention relates to a new electrochromic system having at least one reducible substance and at least one oxidizable substance, OX2 or RED1, interconnected via a binding link. The inventive system is advantageously used in an electrochromic device.

Description

Electrochromic system with coupled RED-OX system and special anions

The present invention relates to an electrochromic system, an electrochromic

Liquid containing this electrochromic system and an electrochromic device containing this electrochromic liquid.

Electrochromic devices containing an electrochromic system are already known.

Such devices usually contain pairs of redox substances as an electrochromic system, which are dissolved in an inert solvent. Conductive salts, light stabilizers and substances that influence the viscosity can also be present.

A reducible and an oxidizable substance are used as the pair of redox substances. Both are colorless or only slightly colored. Under the influence of an electrical voltage, one substance is reduced, the other is oxidized, at least one becoming colored. After switching off the voltage, the two original redox substances re-form, with decolorization or color brightening occurring.

RED., + OX ₂ «" OX ₁ + RED ₂ (colorless) (colored)

(Low energy pair) (high energy pair)

From US-4,902,108 it is known that such pairs of redox substances are suitable in which the reducible substance has at least two chemically reversible reduction waves in the cyclic voltammogram and the oxidizable substance accordingly has at least two chemically reversible oxidation waves.

Electrochromic devices can be used in a variety of ways. For example, they can be designed as an automobile rear-view mirror, which can be darkened by applying a voltage when driving at night and thus prevents glare from headlights of other vehicles (see, for example, US Pat. Nos. 3,280,701, 4,902,108, EP-A-0.435 .689). Furthermore, such devices can also be used in window panes or car sunroofs, where they darken the sunlight after applying a voltage. Ultimately, with such devices A display device can also be constructed for the pictorial representation of information such as letters, numbers and characters.

Electrochromic devices usually consist of a pair of glass or plastic panes, one of which is mirrored in the case of a car mirror. One side of these panes has a translucent, electrically conductive

Layer, e.g. Indium tin oxide (ITO), coated. A cell is now built up from these disks by connecting them with their facing electrically conductive coated side to an annular or rectangular sealing ring, preferably by gluing. The sealing ring creates a uniform distance between the disks, for example 0.1 to 0.5 mm. In these

An electrochromic solution is then poured in via an opening and the cell is sealed. The two panes can be contacted separately via the ITO layer.

The electrochromic systems known from the prior art contain such pairs of redox substances which, after reduction or oxidation, form colored radicals, cation radicals or anion radicals which are chemically reactive. As is known, for example, from Topics in Current Chemistry, Vol. 92, pp. 1-44 (1980), such radicals (ions) can be sensitive to electrophiles or nucleophiles or else radicals. It is therefore necessary to achieve a high stability of an electrochromic device which is such an electrochromic

System that is to survive several thousand switching cycles, ensure that the solvent used is absolutely free of electrophiles, e.g.

Protons, nucleophiles and oxygen. Furthermore, care must be taken to ensure that such reactive species are not formed by electrochemical processes on the electrodes during the operation of the electrochromic device.

The back reaction to RED _j and OX ₂ formulated according to the above reaction equation also takes place continuously during operation of the electrochromic device away from the electrodes within the solution volume. Because of the described dangers of degradation reactions of the radical (ions) by electrophiles, nucleophiles or radicals, it is important for the long-term stability of the display that the

Back reaction according to the above reaction equation can take place as quickly as possible and without side reactions. In such electrochromic devices, segregation of the colored species OX _j and RED ₂ is frequently observed, which leads to a blotchy or streaky coloring of the device. Such segregation is observed, for example, when the device is not horizontal. Current flow over a long period of time can also cause such

Cause segregation. Since in many of the above-mentioned uses of such electrochromic devices, for example in automobile rear-view mirrors, window panes or display devices, the operation preferably takes place in a vertical or almost vertical position and in some cases also over a longer period of time, such segregation leads to serious problems.

It has now been found that such coupling can be largely or completely suppressed by coupling RED _j and OX ₂ via a covalent chemical bond and the presence of certain anions in the electrochromic solution.

The present invention accordingly relates to an electrochromic system containing at least one oxidizable substance RED _l3 which is weakly colored by electron _donation at an anode and at least one reducible substance OX ₂ which is caused by electron absorption at a cathode, with an increase in extinction in the visible range of the spectrum or colorless form changes into a colored form OX _j or RED ₂ , the weakly colored or colorless form being regressed after charge equalization, characterized in that at least one of the substances RED _j and OX ₂ contained are covalently linked to one another via a bridge and that at least one anion type X ^"is contained, which a) has a molar mass> 200 g / mol, preferably> 250 g / mol, and / or b) has a cage-like structure.

A cage-like structure means both closed cages and those which are derived from closed cages by removing 1 to 3 atoms of the cage structure (nest-like shape).

At least one of the transitions RED _j = ≠ OX _j or OX ₂ ^ RED ₂ caused by oxidation or reduction is associated with an increase in extinction in the visible region of the spectrum. The reduction and oxidation processes in the electrochromic system according to the invention generally take place by electron pickup or donation at a cathode or anode, with a potential difference of 0.3 to 3 V preferably prevailing between the electrodes. After the electrical potential has been switched off, a charge equalization takes place spontaneously between the substances RED ₂ and OX, which leads to decolorization or lightening of the color. Such charge equalization also takes place during the current flow in the interior of the electrolyte volume.

The electrochromic system according to the invention preferably contains at least one electrochromic substance of the formula (I)

wherein

Y and Z independently of one another represent a radical OX ₂ or RED _j , wwoobbeeii aabbeerr at least one Y stands for OX ₂ and at least one Z stands for RED _j

in which

OX _{2 stands} for the rest of a reversibly electrochemically reducible redox system, and

RED _{j stands} for the rest of a reversibly electrochemically oxidizable redox system,

B represents a pontic,

c represents an integer from 0 to 5, and

a and b independently of one another are an integer from 0 to 5, preferably are an integer from 0 to 3. The electrochromic system preferably contains at least one electrochromic substance of the formula (I), in which

Y stands for OX ₂ and Z for RED _j and Y and Z alternate in their order.

The electrochromic system according to the invention particularly preferably contains at least one electrochromic substance of the formulas

OX ₂ -B-RED _j (Ia),

OX ₂ -B-RED _j -B-OX ₂ (Ib),

RED _J -B-OX ₂ -B-RED _J (Ic), or

OX ₂ - (B-RED _j -B-OX ₂ ) _d -B-RED _j (Id),

wherein

OX ₂ , RED _j and B have the meaning given above, and

d represents an integer from 1 to 5.

The electrochromic system according to the invention preferably contains at least one anion type X ^" which a) has a molar mass> 200 g / mol, preferably> 250 g / mol and or b) has a cage-like structure, where X ^"

Counter ion of OX ₂ and / or part of an inert conductive salt.

Anions with a cage-like structure mean in particular those which are derived from carbaboranes, very particularly dicarba-nido-undecaborate and dicarba-closododecaborate.

In the event that OX _{2 has} no positive charge, the anion type X ^" contained according to the invention is part of an inert conductive salt.

The anion types X ^" contained in the electrochromic system according to the invention are in particular: C ₁₀ to C ₂₅ alkanesulfonate, preferably C ₁₃ to C ₂₅ alkanesulfonate, C ₃ to C ₁₈ perfluoroalkanesulfonate, preferably C ₅ to C ₁₈ perfluoroalkanesulfonate, C ₁₃ to C ₂₅ alkanoate, by nitro, C ₄ to C ₂₅ alkyl, perfluoro-C _j to C ₈ alkyl, C _j to C ₁₂ alkoxycarbonyl or dichloro substituted benzenesulfonate, optionally substituted by nitro, cyano, hydroxy, C _j to C ₂ alkyl, C _j - to C ₁₂ alkoxy, amino, C _j - to C ₁₂ alkoxycarbonyl or chlorine-substituted naphthalene or biphenyl sulfonate, optionally by nitro, cyano, hydroxy, C _j - to C ₂₅ alkyl, C _τ - bis C ₁₂ -alkoxy, C _j - to C ₁₂ -alkoxycarbonyl or chlorine-substituted benzene, naphthalene or biphenyl disulfonate, by dinitro, C ₆ - to C ₂₅ -alkyl, C ₄ - to C ₁₂ -alkoxycarbonyl, benzoyl, chlorobenzoyl or toluoyl substituted benzoate, the anion of naphthalenedicarboxylic acid, diphenyl ether disulfonate, tetraphenyl borate, cyanotriphenyl borate, tetra-C ₃ - to C ₂₀ -alkoxyborate, tetraphe noxyborate, 7,8- or 7,9-dicarba-nido-undecaborate (1-) or (2-), optionally on the B and / or C atoms by one or two C _j - to C ₁₂ alkyl or phenyl groups are substituted, dodecahydrodicarbadodecaborate (2-) or BC _j - to C ₁₂ -alkyl-C-phenyl-dodecahydrodicarbadodecaborate (1-).

The electrochromic system according to the invention very particularly preferably contains at least one electrochromic substance of the formulas (Ia) - (Id),

wherein

OX _{2 stands} for the remainder of a cathodically reducible substance which, in the cyclic voltammogram, recorded in an inert solvent at room temperature, shows 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,

RED _{j stands} for the rest of the anodically reversibly oxidizable substance, which in the cyclic voltammogram, recorded in an inert solvent at room temperature, shows at least two chemically reversible oxidation waves, the first of these oxidation waves resulting in an increase in the absorbance at at least one wavelength in the visible Area of the electromagnetic spectrum, and

B stands for a pontic. An electrochromic system according to the invention which contains at least one substance of the formula (Ia) - (Id), in which

OX ₂ for a rest of the formulas

2X ^"

4X ^"

2X ^"

2 X ^"

X ^" stands, where

R ² to R ⁵ , R ⁸ , R ⁹ , R ¹⁶ to R ¹⁹ independently of one another C _j to C ₁₈ alkyl, C ₂ to C ₁₂ alkenyl, C ₃ to C ₇ cycloalkyl, C ₇ to C ₁₅ aralkyl or C ₆ to C ₁₀ aryl or

R ⁴ and R ⁵ or R ⁸ and R ⁹ together form a - (CH ₂ ) ₂ - or - (CH ₂ ) ₃ bridge,

R ⁶ , R ⁷ and R ²² to R ²⁵ independently of one another are hydrogen, C _j - to C ₄ -alkyl, C _j - to C ₄ -alkoxy, halogen, cyano, nitro or C _j - to C ₄ -alkoxycarbonyl or

R ²² and R ²³ and / or R ²⁴ and R ^{25 form} a -CH = CH-CH = CH bridge,

R ¹⁰ and R ¹¹ ; R ¹² and R ¹³ ; R ¹⁴ and R ¹⁵ independently of one another represent hydrogen or in pairs a - (CH ₂ ) ₂ -, - (CH ₂ ) ₃ - or -CH = CH bridge,

R ²⁰ and R ²¹ independently of one another are O, N-CN, C (CN) ₂ or NC ₆ - to C _j0 -aryl,

R ²⁶ denotes hydrogen, C _j - to C ₄ -alkyl, C _j - to C ₄ -alkoxy, halogen, cyano, nitro, C _j - to C ₄ -alkoxycarbonyl or C ₆ - to C ₁₀ -aryl, R ⁶⁹ to R ^{74 are} independently hydrogen or C _r C ₆ alkyl, or R ⁶⁹ ; R ¹² and / or R ⁷⁰ ; R ^{13 form} a -CH = CH-CH = CH bridge,

E ¹ and E ^{2 are} independently O, S, NR ¹ or C (CH ₃ ) ₂ or

E ¹ and E ² together form an -N- (CH ₂ ) ₂ -N bridge,

R ¹ C _j - to C _j8 alkyl, C ₂ - to C _j2 alkenyl, C ₄ - to C ₇ cycloalkyl, C ₇ - to C ₁₅ -

Aralkyl, C ₆ -C ₁₀ -aryl means

Z ^{1 is} a direct bond, -CH = CH-, -C (CH ₃ ) = CH-, -C (CN) = CH-, -CC1 = CC1-, -C (OH) = CH-, -CC1 = CH -, -C≡C-, -CH = NN = CH-, -C (CH ₃ ) = NN = C (CH ₃ ) - or -CC1 = NN = CC1-,

Z ² - (CH ₂ ) _r - or -CH ₂ -C ₆ H ₄ -CH ₂ - means

r represents an integer from 1 to 10,

X ^"represents an anion which is redox-inert under the conditions and which a) has a molar mass> 200 g / mol, preferably> 250 g / mol and / or b) has a cage-like structure,

IQO OO where the bond to the bridge member B is via one of the radicals R -R, R -R or, in the case where E ¹ or E ^{2 is} NR ^1, is carried out via R ¹ and the radicals mentioned are then a direct bond,

RED _j for one of the following residues

_R2 8 RR ³³ RR ³² _R 30

R ²⁹ (XVIII),

stands in what

R ²⁸ to R ³¹ , R ³⁴ , R ³⁵ , R ³⁸ , R ³⁹ , R ⁴⁶ , R ⁵³ and R ⁵⁴ independently of one another C _r to

_Are C _j8 alkyl, C ₂ to C ₁₂ alkenyl, C ₃ to C ₇ cycloalkyl, C ₇ to C ₁₅ aralkyl or C ₆ to C _{] 0} aryl, and R ⁴⁶ , R ⁵³ and R ⁵⁴ additionally denotes hydrogen,

R ³² , R ³³ , R ³⁶ , R ³⁷ , R ⁴⁰ , R ⁴¹ , R ⁴² to R ⁴⁵ , R ⁴⁷ , R ⁴⁸ , R ⁴⁹ to R ⁵² and R ⁵⁵ to R ^{57 are} independently hydrogen, C _j - to C ₄ -alkyl, C _j - to C ₄ -alkoxy,

Halogen, cyano, nitro, C _j - to C ₄ -alkoxycarbonyl or C ₆ - to C ₁₀ -aryl and R ⁵⁷ and R ⁵⁸ additionally mean an optionally benzanellated aromatic or quasi-aromatic five- or six-membered heterocyclic ring and R ⁴⁸ additionally NR ⁷⁵ R ⁷⁶ means

R ⁴⁹ and R ⁵⁰ and / or R ⁵¹ and R ⁵² a - (CH ₂ ) ₃ -, - (CH ₂ ) ₄ -, - (CH ₂ ) ₅ - or

-CH = CH-CH = CH bridge,

Z ³ denotes a direct bond, a -CH = CH- or -N = N bridge,

= Z ⁴ = a direct double bond, which means = CH-CH = or = NN = bridge, E ³ to E ⁵ , E ¹⁰ and E ¹¹ independently of one another denote O, S, NR ⁵⁹ or C (CH ₃ ) ₂ and E ⁵ additionally denotes C = O or SO ₂ , or

E ³ and E ⁴ independently of one another mean -CH = CH-,

E ⁶ to E ⁹ independently of one another are S, Se or NR ⁵⁹ ,

R ⁵⁹ , R ⁷⁵ and R ⁷⁶ independently of one another are C _j - to C ₁₂ -alkyl, C ₂ - to C ₈ -alkenyl,

Are C ₃ to C ₇ cycloalkyl, C ₇ to C _{] 5} aralkyl or C ₆ to C ₁₀ aryl and R ^{75 is} additionally hydrogen, or

R ⁷⁵ and R ⁷⁶ in the meaning of NR ⁷⁵ R ⁷⁶ together with the N atom to which they are attached form a five- or six-membered, saturated ring which may contain further heteroatoms,

R ⁶¹ to R ⁶⁸ independently of one another are hydrogen, C _j - to C ₆ -alkyl, C _j - to C ₄ -alkoxy, cyano, C _j - to C ₄ -alkoxycarbonyl or C ₆ - to C ₁₀ -aryl, or

R ⁶¹ ; R ⁶² and R ⁶⁷ ; R ⁶⁸ independently of one another form a - (CH ₂ ) ₃ -, - (CH ₂ ) ₄ - or -CH = CH-CH = CH bridge,

v means an integer between 0 and 10,

wherein the bond to the bridge member B on one of the radicals R ²⁸ -R ^58, R ^61, R ^62, R ^67, R ⁶⁸ or in case that one of the radicals E ³ -E ^π is NR ⁵⁹ R ⁵⁹ occurs and the mentioned residues then stand for a direct bond, and

B for a bridge member of the formulas - (CH ₂ ) _n - or

- [Y ¹ _s (CH ₂ ) _m -Y ² ] ₀ - (CH ₂ ) _p -Y ³ _q -, which are each optionally substituted by C _j - to C ₄ -alkoxy, halogen or phenyl,

Y ¹ to Y ³ independently of one another are O, S, NR ⁶⁰ , COO, CONH, NHCONH, cyclopentanediyl, cyclohexanediyl, phenylene or naphthylene,

R ⁶⁰ C _j - to C ₆ -alkyl, C ₂ - to C ₆ -alkenyl, C ₄ - to C ₇ -cycloalkyl, C ₇ - to C ₁₅ -

Aralkyl or C ₆ to C ₁₀ aryl, n is an integer from 1 to 12,

m and p independently of one another are an integer from 0 to 8,

o is an integer from 0 to 6 and

q and s are independently 0 or 1,

and in the event that OX _{2 has} no positive charge, at least one conductive salt is contained which contains the above-mentioned anion X ^" .

An electrochromic system according to the invention which contains at least one substance of the formula (Ia) - (Id) is very particularly preferred,

wherein

OX _{2 represents} a radical of the formulas (II), (III), (IV) or (V),

in which

R ² , R ³ , R ⁴ , R ⁵ , R ⁸ and R ⁹ independently of one another for C _j - to C ₁₂ -alkyl, C ₂ - to C ₈ -alkenyl, C ₅ - to C ₇ -cycloalkyl, C ₇ - to C ₁₅ aralkyl or C ₆ to C ₁₀ aryl,

R ⁶ and R ⁷ independently of one another represent hydrogen, methyl, ethyl, methoxy, ethoxy, fluorine, chlorine, bromine, cyano, nitro, methoxycarbonyl or ethoxycarbonyl,

R ¹⁰ , R ¹¹ ; R ¹² , R ¹³ and R ¹⁴ , R ¹⁵ independently of one another for hydrogen or, if Z ^{1 is} a direct bond, in each case together for a - (CH ₂ ) ₂ -, - (CH ₂ ) ₃ - or -CH = CH- Stand bridge,

or

R ⁴ , R ⁵ and R ⁸ , R ⁹ independently of one another in pairs together represent a - (CH ₂ ) ₂ - or - (CH ₂ ) ₃ bridge if Z ¹ denotes a direct bond. R ⁶⁹ to R ⁷⁴ are independently hydrogen or C _j -C ₄ alkyl,

E ¹ and E ^{2 are the} same and represent O, S, NR ¹ or C (CH ₃ ) ₂ or together form an -N- (CH ₂ ) ₂ -N bridge,

R ^{1 represents} C _j to C ₁₂ alkyl, C ₂ to C ₄ alkenyl, C ₅ to C ₇ cycloalkyl, C ₇ to C ₁₅ aralkyl or C ₆ to C ₁₀ aryl,

Z ^{1 stands} for a direct bond, -CH = CH-, -C (CH ₃ ) = CH-, -C (CN) = CH-, -C≡C- or -CH = NN = CH-,

Z ^{2 stands} for - (CH) _r - or -CH ₂ -C ₆ H ₄ -CH ₂ -,

r represents an integer between 1 and 6,

X ^" for C ₁₀ to C ₂₅ alkanesulfonate, preferably C ₁₃ to C ₂₅ alkanesulfonate,

C ₃ - to C _j8 -perfluoroalkanesulfonate, preferably C ₅ - to C ₁₈ -perfluoroalkanesulfonate, C ₁₃ - to C ₂₅ -alkanoate, by nitro, C ₄ - to C ₂₅ -alkyl, perfluoro-C _j - to C ₈ -Alkyl, C _j - to C ₁₂ -alkoxycarbonyl or dichloro substituted benzene sulfonate, optionally by nitro, cyano, hydroxy, C, - to C ₂₅ -alkyl, C _j - to C ₁₂ -alkoxy, amino, C _j - to C _12- Alkoxycarbonyl or chlorine substituted naphthalene or biphenyl sulfonate, optionally substituted by nitro, cyano, hydroxy, C to C ₂₅ alkyl, C _j - to C ₁₂ alkoxy, C _τ - to C ₁₂ alkoxycarbonyl or chlorine substituted benzene, naphthalene - or biphenyl disulfonate, benzoate substituted by dinitro, C ₆ - to C ₂₅ -alkyl, C ₄ - to C ₁₂ -alkoxycarbonyl, benzoyl, chlorobenzoyl or toluoyl, the

Anion of naphthalenedicarboxylic acid, diphenyl ether disulfonate, tetraphenyl borate, cyanotriphenyl borate, tetra-C ₃ - to C ₂₀ -alkoxy borate, tetra-phenoxy borate, 7,8- or 7,9-dicarba-nido-undecaborate (l-) or (2-) which are optionally substituted on the B and / or C atoms by one or two C _j - to C _{] 2} -alkyl or phenyl groups, dodecahydrodi- carbadodecaborate (2-) or BC _j - to C ₁₂ -alkyl- C-phenyl-dodecahydro-dicarbadodecaborate (1-), with polyvalent anions such as naphthalenedisulfonate X ^{"representing} one equivalent of this anion, where the bond to the bridge member B is via one of the radicals R ² -R ^π or, in the case where E ¹ or E ^{2 is} NR ^1, is via R ¹ and the radicals mentioned are then a direct bond,

RED _{j represents} a radical of the formulas (X), (XI), (XII), (XIII), (XVI), (XVII), (XVIII) or (XX),

in which

R ²⁸ to R ³¹ , R ³⁴ , R ³⁵ , R ³⁸ , R ³⁹ , R ⁴⁶ , R ⁵³ and R ⁵⁴ independently of one another C _r to C ₁₂ alkyl, C ₂ to C ₈ alkenyl, C ₅ to C ₇ -cycloalkyl, C ₇ - to C ₁₅ aralkyl or C ₆ - to C ₁₀ aryl and

R ⁴⁶ , R ⁵³ and R ⁵⁴ additionally denote hydrogen,

R ³² , R ³³ , R ³⁶ , R ³⁷ , R ⁴⁰ , R ⁴¹ , R ⁴⁷ to R ⁵² , R ⁵⁵ and R ⁵⁶ independently of one another hydrogen, methyl, ethyl, methoxy, ethoxy, fluorine, chlorine, bromine, cyan, nitro , Methoxycarbonyl, ethoxycarbonyl or phenyl and

R ⁵⁷ and R ⁵⁸ additionally denote 2- or 4-pyridyl and

R ⁴⁸ additionally means NR ⁷⁵ R ⁷⁶ ,

Z ³ denotes a direct bond, a -CH = CH- or -N = N bridge,

= Z ⁴ = a direct double bond, which means = CH-CH = or = NN = bridge,

E ³ to E ⁵ , E ¹⁰ and E ¹¹ independently of one another denote O, S, NR ⁵⁹ or C (CH ₃ ) ₂ , but E ³ and E ⁴ have the same meaning,

E ⁶ to E ⁹ are identical to one another and denote S, Se or NR ⁵⁹ and

E ⁵ additionally means C = O,

E ^{6 stands} for NR ⁵⁹ , where R ^{59 means} a direct bond to bridge B and E ⁷ to E ^{9 have} the meaning given above, but need not be identical to one another,

R ⁵⁹ , R ⁷⁵ and R ⁷⁶ independently of one another are C _j to C ₁₂ alkyl, C ₂ to C ₈ alkenyl, C ₅ to C ₇ cycloalkyl, C ₇ to C ₁₅ aralkyl or C ₆ to C ₁₀ aryl, and R ⁷⁵ additionally denotes hydrogen or

R ⁷⁵ and R ⁷⁶ with the meaning NR ⁷⁵ R ⁷⁶ together with the N atom to which they are attached mean pyrrolidino, piperidino or morpholino,

R ^61, R ⁶² and R ^67, R ⁶⁸ are independently hydrogen, C _j - to C ₄ -alkyl, methoxycarbonyl, ethoxycarbonyl or phenyl or in pairs together represent a - (CH ₂₎ ₃ - or - (CH ₂₎ ₄ - Stand bridge,

_R 63 _{to R} 66 _{for hydrogen} _and o

v represents an integer from 1 to 6,

wherein the bond to the bridge member B via one of the radicals R ²⁸ -R ⁴¹ , R ⁴⁶ -R ⁵⁶ , R ⁶¹ , R ⁶² , R ⁶⁷ , R ⁶⁸ or in the event that one of the radicals E ³ -E ^{π stands} for NR ⁵⁹ , takes place via R ⁵⁹ and the radicals mentioned then stand for a direct bond,

B for a bridge member of the formulas - (CH ₂ ) _n -, - (CH ₂ ) _m -O- (CH ₂ ) _p -,

- (CH) _m -NR ⁶⁰ - (CH ₂ ) _p -, - (CH ₂ ) _m -C ₆ H ₄ - (CH ₂ ) _p -, - [O- (CH ₂ ) _p ] ₀ -O-, -ΓNR ⁶⁰ - (CH ₂ ) _P ] _O -NR ⁶⁰ -, - [C ₆ H ₄ - (CH ₂ ) _P ] _O -C ₆ H ₄ -,

- (CH ₂ ) _m -OCO-C ₆ H ₄ -COO- (CH ₂ ) _p -, - (CH ₂ ) _m -NHCO-C ₆ H ₄ -CONH- (CH ₂ ) _p -, - (CH ₂ ) _m -NHCONH-C ₆ H ₄ -NHCONH- (CH ₂ ) _p -,

- (CH ₂ ) _m -OCO- (CH ₂ ) _t -COO- (CH ₂ ) -, - (CH ₂ ) _m -NHCO- (CH ₂ ) _t -CONH- (CH) _p -, - (CH ₂ ) _m -NHCONH- (CH ₂ ) _t -NHCONH- (CH ₂ ) _p -,

R ^{60 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.

An electrochromic system according to the invention which contains at least one substance of the formula (Ia) - (Id) is particularly preferred,

wherein

OX _{2 represents} a radical of the formulas (II), (IV) or (V),

wherein

R> 2, R and R stand for a direct bond to the bridge member B,

R ^J , R ⁵ and R ⁹ independently of one another represent methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, benzyl or phenyl, or in the case of the formulas Ic or Id also stand for a direct bond to the bridge member B,

R ⁶ and R ^{7 are the} same and represent hydrogen, methyl, methoxy, chlorine, cyano or methoxycarbonyl,

R ¹⁰ , R ¹¹ ; R ¹² , R ¹³ and R ¹⁴ , R ¹⁵ independently of one another represent hydrogen or, if Z ¹ denotes a direct bond, in pairs each represent a -CH = CH bridge,

R ⁶⁹ to R ^{72 are the} same and denote hydrogen, methyl or ethyl,

R ⁷³ and R ^{74 are} hydrogen,

E ¹ and E ^{2 are the} same and stand for O or S,

Z ^{1 stands} for a direct bond or -CH = CH-,

X ^" for C ₁₅ - to C ₂₂ alkanesulfonate, C ₅ - to C ₁₂ perfluoroalkanesulfonate, nitrobenzenesulfonate, dinitrobenzenesulfonate, mono- or bis-C ₄ - to C ₁₂ - alkylbenzenesulfonate, dichlorobenzenesulfonate, naphthalenesulfonate, nitronaphthalene sulfonate , Dinitronaphthalenesulfonate, mono- or bis-C ₃ - to C ₁₂ -alkyl- naphthalenesulfonate, Hydroxynaphthalinsulfonat, Aminonaphthalinsulfonat, biphenyl disulphonate, benzenedisulfonate, Nitrobenzoldisulfonat, C ₄ - to C ₁₂ - Alkylbenzoldisulfonat, naphthalene, Nitronaphthalindisulfonat, C ₄ - to C ₁₂ -Alkylnaphthalindisulfonat, Biphenyldisulfonat, dinitrobenzoate, mono- or di-C ₈ - to C ₁₂ - alkyl benzoate, C ₆ - to C ₁₂ alkoxycarbonyl benzoate, benzyl benzoate, toluoyl benzoate, the anion of naphthalenedicarboxylic acid, cyanotriphenyl borate, tetra-C ₃ - to C ₁₂ alkoxyborate, tetraphenoxyborate, 7,8- or 7,9- Dicarba-nido-undecaborate (1-) or (2-), which are optionally substituted on the B and / or C atoms by one or two methyl, ethyl, butyl or phenyl groups, dodeca- hydrodicarbadodecaborate ( 2-) or B-methyl-C-phenyl-dodecahydro-dicarbadodecaborate (1-), where in the case of polyvalent anions such as naphthalenedisulfonate X ^"stands for one equivalent of this anion,

RED _{j represents} a radical of the formulas (X), (XII), (XIII), (XVI) or (XVII),

R ²⁸ , R ³⁴ , R ³⁸ , R ⁴⁶ and R ⁴⁹ stand for a direct bond to the bridge member B,

R ²⁹ to R ³¹ , R ³⁵ and R ³⁹ independently of one another represent methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, benzyl or phenyl, or in the case of the formulas Ib or Id R ³⁰ , R ³⁵ and R ³⁹ also stand for the direct link to bridge member B,

R ³² , R ⁴⁷ and R ^{48 represent} hydrogen,

R ³⁶ , R ³⁷ , R ⁴⁰ , R ⁴¹ and R ⁵⁰ to R ⁵² independently of one another represent hydrogen, methyl, methoxy, chlorine, cyan, methoxycarbonyl or phenyl, or in the case of the formulas Ib or Id R ⁵¹ also for a direct bond to the bridge member B,

Z ^{3 stands} for a direct bond, a -CH = CH- or -N = N bridge,

= Z ⁴ = stands for a direct double bond, a = CH-CH = or = NN = bridge,

E ³ to E ⁵ independently of one another represent O, S or NR ⁵⁹ , but E ³ and E ⁴ have the same meaning, E ⁶ to E ⁹ are identical to one another and stand for S, Se or NR ⁵⁹ ,

R ^{59 represents} methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, benzyl or phenyl, or in the case of the formula XVI in Ib or Id also represents a direct bond to the bridge member B,

- (CH ₂ ) _m -NR ⁶⁰ - (CH ₂ ) _p -, - (CH ₂ ) _ra -C ₆ H ₄ - (CH ₂ ) _p -, -O- (CH ₂ ) _p -O-, -NR ⁶⁰ - (CH ₂ ) _p -NR ⁶⁰ -,

- (CH ₂ ) _m -OCO-C ₆ H ₄ -COO- (CH ₂ ) _p -, - (CH ₂ ) _m -NHCO-C ₆ H ₄ -CONH- (CH ₂ ) _p -, - (CH ₂ ) _m -NHCONH-C ₆ H ₄ -NHCONH- (CH ₂ ) _p -, - (CH ₂ ) _m -OCO- (CH ₂ ) _t -COO- (CH ₂ ) _p -, - (CH ₂ ) _m - NHCO- (CH ₂ ) _t -CONH- (CH ₂ ) _p -,

- (CH ₂ ) _m -NHCONH- (CH ₂ ) _t -NHCONH- (CH ₂ ) _p -,

R ^{60 represents} methyl,

n represents an integer from 1 to 10,

m and p are the same and represent an integer from 0 to 2 and

t represents an integer from 1 to 6.

An electrochromic system according to the invention which contains at least one substance of the formula (Ia) corresponding to one of the formulas is very particularly preferred

(XXIII),

(XXVIII),

(XXIX),

contains, or at least one substance of formula (Ib) according to one of the formulas

(XXXII),

or at least one substance of the formula (Ic) according to one of the formulas

(XXXVII),

(XLII),

woπn

R ³ , R ⁵ , R ³⁵ and R ³⁹ independently of one another represent methyl, ethyl, propyl, butyl, pentyl, hexyl or benzyl,

R ⁶ , R ⁷ and R ³⁶ , R ³⁷ are identical in pairs and represent hydrogen, methyl, methoxy, chlorine, cyano or methoxy carbonyl,

R ¹² and R ^{13 represent} hydrogen or, if Z ¹ denotes a direct bond, together represent a -CH = CH bridge,

R ⁶⁹ to R ^{72 are the} same and represent hydrogen or methyl,

E ¹ and E ^{2 are the} same and stand for O or S, Z ^{1 stands} for a direct bond or -CH = CH-,

R ³² , R ⁴⁷ and R ^{48 represent} hydrogen,

E ³ to E ⁵ independently of one another represent O, S or NR ⁵⁹ , but E ³ and E ⁴ are the same,

R ²⁹ to R ³¹ and R ⁵⁹ independently of one another are methyl, ethyl, propyl, butyl,

Are pentyl, hexyl or benzyl, where R ²⁹ to R ^{31 are} preferably the same,

R ⁴⁰ and R ^{41 are the} same and represent hydrogen, methyl, ethyl, propyl, butyl or phenyl,

Z ^{3 represents} a direct bond, -CH = CH- or -N = N-,

R ⁵⁰ to R ⁵² independently of one another represent hydrogen, methyl, methoxy, chlorine, cyano, methoxycarbonyl, ethoxycarbonyl or phenyl, but are preferably the same,

E ⁶ to E ⁹ are identical to one another and stand for S, Se or NR ⁵⁹ ,

Z ^{4 stands} for a direct double bond, a = CH-CH = or = NN = bridge,

m represents an integer from 1 to 5,

u stands for 0 or 1 and

X ^" for C _{] 5} - to C ₂₀ alkanesulfonate, C ₅ - to C ₈ perfluoroalkanesulfonate, mono- or dibutylbenzenesulfonate, mono- or di-tert-butylbenzenesulfonate, octylbenzenesulfonate, dodecylbenzenesulfonate, naphthalenesulfonate sulfonate, biphenyl sulfonate, biphenylbenzene sulfonate , Dibutylnaphthalenesulfonate, biphenyldisulfonate, benzoyl benzoate, cyanotriphenylborate, tetra- C ₃ - to C ₈ -alkoxyborate, tetraphenoxyborate, 7,8- or 7,9-dicarba- nido- undecaborate (l-) or (2-) or dodecahydro- dicarbadodecaborate (2-), with polyvalent anions such as naphthalene disulfonate X ^" for

Equivalent to this anion. In the abovementioned substituent meanings, alkyl radicals, including modified ones, such as, for example, alkoxy or aralkyl radicals, are preferably those with 1 to 12 carbon atoms, in particular with 1 to 8 carbon atoms, unless stated otherwise. They may be straight or branched and optionally further substituents bear substituents such as C _j - to C ₄ -alkoxy, fluorine, chlorine, hydroxy, cyano, C _j - to C ₄ -alkoxycarbonyl or COOH.

Cycloalkyl radicals are preferably understood to mean those having 3 to 7 carbon atoms, in particular 5 or 6 carbon atoms.

Alkenyl radicals are preferably those with 2 to 8 carbon atoms, in particular 2 to 4 carbon atoms.

Aryl residues, including those in aralkyl residues, are preferably phenyl or naphthyl residues, in particular phenyl residues. They can be substituted by 1 to 3 of the following radicals: C _j - to C ₆ -alkyl, C _j - to C ₆ -alkoxy, fluorine, chlorine, bromine, cyano, hydroxy, C _j - to C ₆ -alkoxycarbonyl or nitro . Two adjacent residues can also form a ring.

The compounds of the formula (I) are known in principle from the unpublished German Application No. 19605451.6 and can be prepared as described there.

Compounds of the formula (I) which contain the anion X ^" defined above as a counterion are new and are also an object of the present invention.

The electrochromic compounds of formula (I) obtained according to WO 97/30 134 do not carry any anions X ^" according to the invention due to their synthesis. These anions X ^" must be introduced by anion exchange. This exchange can take place, for example, in solvents in which the compounds of the formula (I) with the anions caused by the synthesis are moderately to readily soluble

Compounds of formula (I) with the anions according to the invention are poorly soluble. The compounds of the formula (I) with the anions caused by the synthesis are then added together with salts of the anions according to the invention, for example. the alkali metal or tetraalkylammonium salts listed below under conductive salts in such solvents and stirred at room temperature to the reflux temperature of the solvent, the desired compounds of the formula (I) with the anions according to the invention precipitate and are suctioned off. Suitable solvents are, for example, alcohols such as methanol, ethanol; Water; Nitriles such as acetonitrile or mixtures thereof.

Another method is to work in a two-phase mixture, the compounds of the formula (I) being dependent on the synthesis

Anions and the alkali metal or tetraalkylammonium salts of the anions X ^" according to the invention should be at least partially soluble in one solvent, but the compounds of the formula (I) with the anions X ^" according to the invention should be readily soluble in the other solvent. This mixture is then stirred at room temperature to the reflux temperature of the solvent mixture and separated. By distilling off the second solvent, the compounds of formula (I) with the anions X ^" according to the invention are obtained. Suitable solvent pairs are, for example, water / toluene, water / methylene chloride, water / butanone.

A third possibility is the use of ion exchangers.

The electrochromic system according to the invention preferably contains at least one solvent, whereby an electrochromic liquid is formed, which is also the subject of the present invention.

Suitable solvents are all solvents which are redox-inert under the selected voltages and which cannot release any electrophiles or nucleophiles or which themselves react as sufficiently strong electrophiles or nucleophiles and could thus react with the colored radical ions. Examples are propylene carbonate, γ-butyrolactone, acetonitrile, propionitrile, glutaronitrile, methylglutaronitrile, 3,3'-oxydipropionitrile, hydroxypropionitrile, dimethylformamide, N-methylpyrrolidone, sulfolane, 3-methylsulfolane or mixtures thereof. Propylene carbonate and mixtures thereof with glutaronitrile or 3-methylsulfolane are preferred.

The electrochromic liquid according to the invention can contain at least one inert conductive salt. It must contain a conductive salt if OX _{2 is} not cationic.

Lithium, sodium and tetraalkylammonium salts are suitable as inert conductive salts, in particular the latter. The alkyl groups can have between 1 and 18 carbon atoms and can be the same or different. Tetrabutylammonium is preferred. Anions of these salts are the above-mentioned anions X ^" in their general, special or very special meaning.

The conductive salts are preferably used in the range from 0 to 1 molar.

Thickeners can be used as further additives to the electrochromic liquid in order to control the viscosity of the liquid. The ^* can be used to control the bleaching speed after switching off the power.

Suitable thickeners are all the usual for this purpose compounds such as polyacrylate, polymethacrylate (Luctite L ^®), polycarbonate and polyurethane are suitable.

The electrochromic liquid can also be in the form of a gel.

UV absorbers are used as additional additives for the electrochromic liquid

Improving lightfastness in question. Examples are Uvinul ^® 3000 (2,4-dihydroxybenzophenone, BASF), SANDUVOR ^® (benzophenone 2-hydroxy-4-n-octyloxy, Clariant) 3035, Tinuvin ^® 571 (2- (2H-benzotriazol-2-yl) - 6-dodecyl-4-methylphenol, Ciba), Cyasorb 24 ™ (2,2'-dihydroxy-4-methoxybenzophenone, American Cyanamid Company), Uvinul ^® 3035 (ethyl 2-cyano-3,3-diphenyl acrylate, BASF ), Uvinul ^® 3039 (2-ethylhexyl-2-cyano-3,3-diphenylacrylate, BASF), UVINUL ^® 3088 (2-ethylhexyl p-methoxycinnamate, BASF), CHIMASSORB ^® 90 (2-Hy droxy-4-methoxybenzophenone , Ciba).

The UV absorbers are used in the range of 0.01 to 2 mol / 1, preferably 0.04 to 1 mol / 1.

The electrochromic liquid according to the invention contains the substances of the formula (I), in particular of the formulas (Ia) to (Id), in each case in a concentration of at least 10 ^"4 mol / 1, preferably 0.001 to 1 mol / 1. Mixtures of several can also be used electrochromic substances of the formula (I) are used.

The electrochromic liquids according to the invention are ideally suited as part of an electrochromic device. The present invention accordingly furthermore relates to electrochromic devices containing an electrochromic liquid according to the invention. The construction of an electrochromic device, for example as a window pane, car sun roof, automobile rear view mirror or display can be formed is known in principle. The electrochromic device according to the invention consists of two mutually facing, translucent glass or plastic panes, one of which may be mirrored and the mutually facing sides of which are coated in an electrically conductive manner, for example with indium tin oxide (ITO), between which there is the electrochromic liquid according to the invention located. The following are also suitable as conductive materials: antimony-doped tin oxide, fluorine-doped tin oxide, antimony-doped zinc oxide, aluminum-doped zinc oxide, tin oxide; also conductive organic polymers such as optionally substituted polythienyls, polypyrroles, polyanilines, polyacetylene. In the event that one of the panes is mirrored, this can also be used as a conductive

Layer can be used. The distance between the two disks is generally 0.005-2 mm, preferably 0.02-0.5 mm. The desired distance between the washers is generally established by a sealing ring.

In the event that the electrochromic device is an electrochromic display device, at least one of the two conductive layers or both are divided into segments which are electrically separated from one another and which are contacted individually.

However, only one of the two plates can be conductively coated and divided into segments. The segments can be separated, for example, by mechanical removal of the conductive layer, for example by scratching,

Scratching, scraping or milling or by chemical means, for example by etching using, for example, a hydrochloric acid solution of FeCl ₂ and SnCl ₂ . This removal of the conductive layer can be done using masks, e.g. B. those made of photoresist, locally controlled. But it can also be the electrically separated segments by targeted, for. B. by means of masks, application, z. B. sputtering or printing, the conductive layer. The segments are contacted, for example, by means of fine strips of conductive material, with which the segment is electrically conductively connected to a contact on the edge of the electrochromic device. These fine contact strips can either consist of the same material as the conductive layer itself and, for example, of the same

Can be divided into segments as described above. But you can also z. B. to improve the conductivity of other material such as fine metallic conductors, for example made of copper or silver. A combination of metallic material and the material of the conductive coating is also possible. These metallic conductors can, for example, neither applied in fine wire form, e.g. B. glued, or be printed. All of the techniques just described are generally known from the manufacture of liquid crystal displays (LCD).

The displays can be viewed in transmitted light or reflectively via a mirror.

The two plates are placed on top of one another with the sides facing one another, conductively coated and divided into segments, separated by, for example, a sealing ring and bonded to one another at the edge. The sealing ring can be made, for example, of plastic or thin glass or another material that is inert to the electrochromic liquid. The distance between the plates can also be established by means of other spacers, for example small plastic or glass beads or certain sand fractions, in which case these spacers are applied together with the adhesive and then together form the sealing ring. The sealing ring contains one or two recesses which are used to fill the electrochromic device. The distance between the two plates is between 0.005 and 2 mm, preferably 0.02 to 0.5 mm. In the case of large-area display devices, in particular those made of plastic, it can be advantageous to use spacers, for example plastic spheres of the same diameter, which are distributed over the surface of the display device, to determine the distance between the

Keep plates constant.

This display device is filled with an electrochromic liquid through the openings in the sealing ring, whereby work must always be carried out with the exclusion of moisture and oxygen. Filling can take place, for example, by means of fine cannulas or else using the vacuum filling technique, in which the device and the liquid, filled into a flat bowl, are introduced into an evacuable container. This is evacuated. Then the display device, which contains only one filling opening, is immersed in the liquid with this opening. When the vacuum is removed, the liquid is now pressed into the display device.

If such electrochromic devices are placed upright in the switched-on state, there is no separation of the color shades of the colored species formed on the anode and cathode, for example even after several hours or days OXJ-B-REDJ and RED ₂ -B-OX ₂ . The devices are evenly colored, show no stains or streaks and bleach out quickly and evenly after the power is switched off. If, on the other hand, electrochromic compounds of the formula (I) are used whose anion is not an anion X ^" according to the invention, for example tetrafluoroborate, a clear color separation is obtained after a short time, for example after 1 hour, in the upright electrochromic device. For example, on A blue stripe at the upper end and a yellow stripe at the lower end, while the expected mixed color green is observed in the middle. After switching off the voltage, only the middle zone fades quickly, while the upper and lower zones continue for a long time, eg several

Stay colored for hours. The same observation is made in the case of electrochromic compounds of the formula (I), the OX _{2 of which is} not cationic and thus does not carry an anion, but which are used in an electrochromic liquid, the conductive salt of which contains an anion not according to the invention, for example tetrafluoroborate.

In electrochromic displays, e.g. Segment displays can be found at

Use of the electrochromic compounds or liquids according to the invention, even after a long period of operation in the upright position of the device, likewise no color separation within the segment and rapid and complete deletion after switching off the current, while the use of the above-mentioned electrochromic substances or liquids for color separation and very slow deletion of these separate color areas results. Especially with display devices, it often happens that individual segments are switched on for a long time, but nevertheless have to quickly fade when the information to be displayed changes. The electrochromic compounds and liquids according to the invention clearly show here

Advantages over those which do not contain any anions according to the invention.

The self-extinguishing single-cell electrochromic device according to the invention can also contain others in addition to the electrochromic substances of the formulas (I) described above, in particular the formulas (Ia) to (Id), as described, for example, in US Pat. No. 4,902,108, Topics in Current Chemistry, Vol 92, pp. 1-44

(1980) and Angew. Chem. 90, 927 (1978). Such electrochromic substances originate, for example, from the groups given above under formulas (II) to (XX), in which case none of the radicals mentioned can have the meaning "direct bond to bridge B". Other suitable electrochromic substances are, for example, tetrazolinium salts or Salts or complexes of metal ions, eg [Fe (C ₅ H ₅ ) ₂ ] ^{0/1 +} . Addition of such redox systems can be advantageous, for example, in order to correct or intensify the color tone, for example of the display, when the electrochromic device according to the invention is switched on.

The anions of such electrochromic mixed components are said to mean

X ^" in its general, special and very special meaning listed above.

Examples:

example 1

Production of an electrochromic substance of formula (I)

a) 5.0 g of 4,4'-dipyridyl were dissolved in 30 ml of anhydrous acetonitrile at 50 ° C. 2.7 g of benzyl bromide were added dropwise at this temperature over 50 minutes. After 3 h at 50 ° C., the mixture was cooled and the light yellow precipitate was filtered off with suction. This was washed with 60 ml of toluene and dried in vacuo. 3.9 g (75% of theory) of the product of the formula were obtained

Br ^"

b) 10.1 g of phenothiazine were dissolved in 60 ml of anhydrous N-methylpyrrolidone under an N ₂ atmosphere at room temperature. 5.9 g of potassium tert-butoxide were added. An orange suspension was formed while heating to 30 ° C., which was stirred at 30 ° C. for 30 min. Then 54 g of 1,4-dibromobutane was added all at once. The temperature rose to 53 ° C. The mixture was heated to 70 ° C. for 45 minutes, at 15 minutes at this

Maintained temperature and then cooled. The light brown suspension was added to 1 liter of water. The mixture was extracted with 3x200 ml of toluene, the extract was washed with 5x200 ml of water, dried over sodium sulfate and concentrated on a rotary evaporator. The oily residue was dissolved in 400 ml of hexane, filtered from the insoluble and concentrated again. The excess 1,4-dibromobutane was then distilled off at 0.1 to 0.5 mbar. 9.6 g (57% of theory) of a reddish-yellow, viscous oil of the formula were obtained

c) 3.7 g of the phenothiazine of the formula (LXV) were dissolved in 10 ml of anhydrous N-methylpyrrolidone at room temperature under an N ₂ atmosphere. 1.8 g of the dipyridinium salt of the formula (LXIV) were added. The suspension was heated to 80 ° C. for 1 h and held at this temperature for a total of 13 h. The suspension became thicker and thicker. After cooling to room temperature, the product was filtered off with suction and washed with 5 ml of N-methylpyrrolidone. The hygroscopic raw product of the formula

with X ^" = Br ^" was dissolved in 7 ml of methanol and filtered. 3.0 g of sodium cyanotriphenylborate were sprinkled into the filtrate for 2 h. A precipitate slowly formed, which was completed by stirring at room temperature for 18 h. Finally, the product was filtered off with suction, washed with methanol until it was colorless and dried in vacuo. 0.5 g (13% of theory) of pale bluish powder of the formula (LXVI) with X ^" = NC-B (C ₆ H ₅ ) ₃ ^{" was obtained} .

In an electrochromic device according to Example 29-30, a violet-blue coloration with λ _maχ = 517 and 606 nm was achieved.

Example 2

a) 9.2 g of phenazine were suspended in 60 ml of anhydrous tetrahydrofuran under a nitrogen atmosphere. 30.8 ml dripped over 15 minutes

20% by weight phenyllithium solution in cyclohexane / diethyl ether 7: 3, the temperature at max. Was held at 35 ° C. The solution was

Stirred for 30 min at room temperature.

At 15 ° C, 30.2 ml of 1,4-dibromobutane were added in one portion. The temperature rose to 38 ° C. After 6 h at room temperature, 200 ml of water were added and the pH was adjusted to 7.0. The organic phase was separated, washed three times with 100 ml of water and concentrated in vacuo. Finally, excess 1,4-dibromobutane was distilled off at a pressure of 0.2 mbar. The oily residue was dissolved hot in 400 ml of ethanol. The product which precipitated after cooling was filtered off with suction, washed with ethanol and hexane and dried. 8.0 g (41% of theory) of pale yellow powder of 9,10-dihydrophenazine of the formula were obtained

(LXVII).

b) 7.5 g of the 9,10-dihydrophenazine of the formula (LXVII) from a) and 6.1 g of 4,4'-dipyridyl were in 100 ml of acetonitrile at 70 ° C. for 24 hours

Stirred nitrogen atmosphere. After cooling, the product was filtered off with suction and washed with 50 ml of acetone. After drying, 6.3 g (60% of theory) of the salt of the formula were obtained

(LXVIII)

c) 6.1 g of the salt obtained under b) were stirred in 70 ml of N-methyl-2-pyrrolidone together with 2.7 ml of benzyl bromide for 7 hours at 70 ° C. under a nitrogen atmosphere. After cooling, the mixture was diluted with 150 ml of toluene and the precipitated product was filtered off with suction. It was washed thoroughly with 150 ml of toluene and 500 ml of hexane and dried. 5.5 g (69% of theory) of the dipyridinium salt of the formula were obtained with X ^" = Br ^" .

d) 4.0 g of this product from c) were introduced into a two-phase mixture of 70 ml of water and 70 ml of toluene under a nitrogen atmosphere. 3.6 g of sodium dodecylbenzenesulfonate was added. The mixture was stirred at 50 ° C. for 2 h and cooled. A clear two-phase system developed from the initial cloudy mixture. The toluene phase was separated and evaporated to dryness in vacuo. 6.7 g of a sticky, pale greenish product of the formula (LXIX) with X ^" = C ₁₂ H ₂₅ -C ₆ H ₄ -SO ₃ ^{" were obtained} .

In an electrochromic device according to Example 29-31, a greenish-blue coloration with λ _max = 466 and 407 nm was achieved.

Example 2a (comparative example)

4.0 g of this product from Example 2 c) were dissolved in 100 ml of methanol at 65 ° C. under a nitrogen atmosphere. 7.4 g of tetrabutylammonium tetrafluoroborate were sprinkled in over the course of 5 minutes. A precipitation occurred. After 5 min at 65 ° C., the mixture was cooled, suction filtered, washed with 200 ml of methanol and 50 ml of hexane and dried in vacuo. 3.4 g (83% of theory) of pale beige powder of the formula (LXIX) with X ^" = BF ₄ ^{" were obtained} .

In an electrochromic device according to Example 29-30, a greenish-blue coloration with λ _max = 466 and 407 nm was achieved.

Example 3

a) 45.3 g of 2-methylthiobenzothiazole were dissolved in 75 ml of toluene. 151 ml of 1,4-dibromobutane and a spatula tip of potassium iodide were added. The mixture was boiled for 4 hours and then cooled. It was filtered and washed with 50 ml of toluene. The filtrate was heated to 50 ° C and with 35.9 ml Dimethyl sulfate added. The mixture was stirred at 50 ° C. for 8 h, cooled, suction filtered and washed with 250 ml of toluene. The product was stirred in 100 ml of acetone, suction filtered again and washed with 300 ml of acetone. After drying in vacuo, 53.1 g (50% of theory) of the salt of the formula were obtained

6.95 g of the benzothiazolium salt of the formula (LXX) from a) and 2.9 g of the hydrazone of the formula were added to 60 ml of acetonitrile under a nitrogen atmosphere

(from Aldrich Chemical Company Ltd., England). 2.3 ml of triethylamine were added at room temperature. A solution was briefly formed, then a precipitate formed. After 5 h at room temperature, the product was finally filtered off with suction, washed with 50 ml of methanol, 100 ml of water and a further 50 ml of methanol until the process was colorless and dried in vacuo. 6.0 g (83% of theory) of the azine of the formula were obtained (LXXII).

c) If the procedure was analogous to Example 1 a), but 6.8 ml of butyl bromide were used instead of benzyl bromide, 5.2 g (57% of theory) of the pyridinium salt of the formula were obtained

(LXXIII).

d) 2.0 g of the azine of the formula (LXXII) from b) and 1.3 g of the pyridinium salt of the formula (LXXIII) from c) were in 20 ml of N-methyl-2-pyrrolidone under a nitrogen atmosphere for 102 h at 80 ° C. touched. After cooling, a greenish crystalline product was filtered off and washed with 50 ml of acetone. After drying, 0.25 g (7.6% of theory) of the dipyridinium salt of the formula was obtained

(LXXIV)

with X ^" = Br ^" e) 0.25 g of the product from c) were almost completely dissolved in 5 ml of methanol. 0.45 g sodium cyanotriphenyl borate was added. The mixture was stirred at room temperature for 17 h, during which the product gradually became crystalline. It was suction filtered, washed with 25 ml of methanol, 25 ml of water and again with 25 ml of methanol. After drying, 0.15 g was obtained

(59% of theory) light gray powder of the formula (LXXTV) with X ^" = NC-B (C ₆ H ₅ ) ₃ ^" .

In an electrochromic device according to Example 29-30, a green color with λ _maχ = 402; 606; 734 nm achieved.

Example 4

a) 4.0 g of the phenothiazine of the formula (LXV) from Example 1b) and 0.95 g of 4,4'-dipyridyl were stirred in 10 ml of acetonitrile under a nitrogen atmosphere at 70 ° C. for 9 h. The suspension was then diluted with 10 ml of N-methyl-2-pyrrolidone and stirred for 25 h at 70 ° C. and 7 h at 80 ° C. After cooling, was filtered off, washed with 50 ml of methanol and in

Vacuum dried. 1.6 g (32% of theory) of the dipyridinium salt of the formula were obtained

with X ^" = Br ^" .

b) 1.4 g of the salt of the formula (LXXV) from a) were added in 20 ml of methanol

Reflux partially resolved. 2.5 g of sodium tetraphenyl borate was added. The mixture was boiled for a further 5 minutes and then stirred cold. The precipitated product was filtered off, washed with 50 ml of methanol, 50 ml of water and again with 50 ml of methanol and dried in vacuo. You got 1.1 g (77% of theory) dipyridinium salt of the formula (LXXV) with X ^" = B (C ₆ H ₅ ) ₄ ^" .

In an electrochromic device according to Example 29-30, a violet-blue coloration with λ _max = 517 and 606 nm was achieved.

The following examples were produced quite analogously.

Example 29

A cell was constructed from two indium tin oxide (ITO) coated glass plates and a sealing ring, as described in US Pat. No. 4,902,108. It was filled under a nitrogen atmosphere through an opening in the sealing ring with a solution containing 0.03 molar of the electrochromic substance of the formula (LXXTV) with X ^Θ = NC-B (C ₆ H ₅ ) ₃ ^Θ according to Example 3, in anhydrous Glutaronitrile was. The cell was sealed airtight. The solution in the cell was pale yellow. After applying a voltage of 1.5 V, the solution quickly turned intensely green; after switching off the voltage, the cell contents completely decolorized within 1 min. The cell was decolorized more quickly by short-circuiting.

If the cell was placed vertically, the green color was uniformly intensive over the entire cell area even after 3 hours of operation at 1.5 V. After switching off and short-circuiting, the cell decolorized quickly and evenly over its entire surface.

Example 30

A cell was built as in Example 29. However, one of the glass plates was mirrored on the side facing away from the ITO layer.

It was filled under a N ₂ atmosphere with a solution which was 0.03 molar of the electrochromic substance of the formula (LXIX) with X ^Θ = C _j2 H ₂₅ -C ₆ H ₄ -SO ₃ ^Θ according to Example 2 in anhydrous propylene carbonate . The color of the solution in the cell was pale yellow. After applying a voltage of 0.9 V, the solution quickly turned deep greenish blue, after switching off the power supply and short-circuiting, the cell content decolored again within approx. 10 s and resulted in the original pale yellow. More than 100,000 such switching cycles were survived without any changes.

If the cell was placed vertically, the green color was uniformly intensive over the entire cell area even after 3 days of operation at 0.9 V. After switching off and short-circuiting, the cell decolorized evenly over its entire area for 10 s. Example 30 a (comparative example)

The procedure was as described in Example 30. However, the electrochromic substance of the formula (LXIX) with X ^" = BF ₄ ^" according to Example 2a was used. The color of the solution in the cell was pale yellow. After applying a voltage of 0.9 V, the solution quickly turned deep greenish blue, after switching off the power supply and short-circuiting, the cell content decolored again for 10 s and resulted in the original pale yellow. More than 100,000 such switching cycles were survived without any changes.

If the cell was placed vertically, a blue streak formed within 1 hour on the upper edge of the cell and a greenish-yellow stripe on the lower edge of the cell, while the middle cell zone remained colored blue. This condition remained even after a long period of operation. The two strips each formed approximately 1/4 of the cell height. After switching off and short-circuiting, the cell decolorized in the middle cell zone for 10 s. The blue and greenish yellow stripes on the top and bottom, however, remained. These were only after 2 - 3 hours

Stripes also completely faded.

Example 31

A glass plate coated with ITO was coated with a commercially available photoresist, e.g. B. Positive 20 from Kontakt Chemie, Iffezheim, sprayed on the coated side and dried in the dark at 50 to 70 ° C for 1 h. The lacquer layer was then covered with a film which, as shown in Figure 1, contained black segments in a transparent environment. This film was printed with a laser printer according to a template produced on the computer. This film was used to coat the photoresist layer with UV light (from a mercury lamp, e.g. HBO 200W / 2 from Osram or from a xenon high-pressure lamp XBO

75W / 2 from Osram) exposed for 1 to 5 min. The film was removed and the lacquer layer was treated in a sodium hydroxide solution (7 g sodium hydroxide per liter of water) so that the exposed areas were rinsed off. The glass plate prepared in this way was then placed in a bath of 67 g FeCl ₂ × 4 H ₂ O, 6 g SnCl ₂ × 2 H ₂ O, 104 ml water and 113 ml 37% by weight. Hydrochloric acid, causing the

ITO layer was removed at the paint-free, previously exposed areas. The remaining lacquer layer was removed with acetone. This gave a glass plate (1) which carried segments (4), conductor connections (3) and contacts (2). A rectangular ring was cut out of a 0.2 mm thick polyethylene film. An approximately 1-2 cm long piece was removed from one of its long sides (5). This film was then placed on the ITO-coated side of a second glass plate (7). Outside the film - with the exception of the opening (6) - a two-component adhesive, for example UHU ^® plus endfest 300 from Fa.

UHU GmbH, Bühl in Baden, spread out. Now the etched glass plate (1) produced as described above was placed on the film in such a way that the ^" ITO layer was on the side of the film (see Figure 2). The two-component adhesive was then allowed to harden, possibly by gentle heating to approx 40 ° C.

The cell was then exposed to a solution of. Under a nitrogen or argon atmosphere

220 mg of the electrochromic compound of the formula

in 10 ml of anhydrous propylene carbonate, which was prepared under a nitrogen or argon atmosphere, filled through the opening (6), for example with the aid of a fine pipette or by drawing in the solution in vacuo. The filling opening (6) was now filled with a suitable piece of polyethylene film and sealed with two-component adhesive.

By applying a voltage of 0.8 V to the contacts (2) of the segments as the cathode and the non-etched second plate (7) as the anode, a deep greenish blue image of the contacted segments quickly formed. All of them were able to use 7

Letters and numbers that can be represented in segments are generated in a deep greenish blue on a pale yellow background. By switching off the voltage and short-circuiting the contacts, the picture quickly disappeared again.

If this cell was placed vertically, the switched segments remain monochrome even after several hours of operation without any other colored edge strips.

After switching off the voltage and short-circuiting, the segments decolorized quickly and evenly. Analogously to Examples 29-31, electrochromic cells were built up using the electrochromic substances listed in Examples 1-28, and similarly good results were achieved.

Claims

claims

1. Electrochromic system containing at least one oxidizable substance RED _j , which is due to electron donation at an anode and at least one reducible substance OX ₂ , which is due to electron acceptance at a cathode, with increasing extinction in the visible region of the spectrum from a weakly colored or colorless form changes into a colored form OX _j or RED ₂ , the weakly colored or colorless form regressing after charge equalization, characterized in that at least one of the substances RED _j and OX ₂ contained are covalently linked to one another via a bridge,

and that at least one anion type X ^"is contained, which a) has a molar mass> 200 g / mol, preferably> 250 g / mol, and / or b) has a cage-like structure.

2. Electrochromic system according to claim 1, characterized in that the anion type X ^" counterion of OX ₂ and / or part of an inert

Leitsalzes is.

3. Electrochromic system according to claims 1 and 2, characterized in that the anion type X ^"is part of an inert conductive salt, in the event that OX _{2 has} no positive charge.

4. Electrochromic system according to claims 1 to 3, characterized in that the anion sites X ^" C ₁₀ - to C ₂₅ alkanesulfonate, preferably C ₁₃ - to C ₂₅ alkanesulfonate, C ₅ - to C ₁₈ perfluoroalkanesulfonate, preferably C ₄ - to C _j8 perfluoroalkanesulfonate, C _j3 to C ₂₅ alkanoate, benzenesulfonate substituted by nitro, C ₄ to C ₂₅ alkyl, perfiuor C _j to C ₈ alkyl, C _j to C ₁₂ alkoxycarbonyl or dichloro , optionally by nitro, cyano,

Hydroxy, C _j - to C ₂₅ alkyl, C _j - to C ₁₂ alkoxy, amino, C _j - to C ₁₂ alkoxycarbonyl or chlorine-substituted naphthalene or biphenyl sulfonate, optionally by nitro, cyano, hydroxy, C _j - to C ₂₅ -alkyl, C _j - to C ₁₂ -alkoxy, C _j - to C ₁₂ -alkoxycarbonyl or chlorine-substituted benzene, naphthalene or biphenyl disulfonate, by dinitro, C ₆ - to C ₂₅ -

Alkyl, C ₄ - to C ₁₂ -alkoxycarbonyl, benzoyl, chlorobenzoyl or toluoyl substituted benzoate, the anion of naphthalenedicarboxylic acid, diphenyl ether disulfonate, tetraphenylborate, cyanotriphenylborate, tetra-C ₃ - to C ₂₀ -alkoxyborate, tetraphenoxyborate, 7,8- or 7,9-dicarba-nido-undecaborate (1-) or (2-), which may be attached to the B- and / or C atoms are substituted by one or two C _j - to C ₁₂ -alkyl or phenyl groups, dodecahydrodicarbadodecaborate (2-) or BC _j - to C ₁₂ -alkyl-C-phenyl-dodecahydrodicarbadodecaborate (l-) is contained .

5. Electrochromic system according to claims 1 to 4, characterized in that there is at least one electrochromic substance of the formula (I)

wherein

Y and Z independently of one another are OX ₂ or RED _j , but at least one Y is OX ₂ and at least one Z is RED _j ,

in which

B represents a pontic,

c represents an integer from 0 to 5, and

a and b independently of one another represent an integer from 0 to 5.

6. Electrochromic system according to claims 1 to 5, characterized in that it contains at least one electrochromic substance of the formula (I), in which Y is OX ₂ and Z is RED _j and Y and Z alternate in their sequence.

7. Electrochromic system according to claims 1 to 6, characterized in that there is at least one electrochromic substance of the formulas

OX ₂ -B-RED _j (la),

OX ₂ -B-RED _j -B-OX ₂ (Ib),

RED _j -B-OX ₂ -B-RED, (Ic), or

OX ₂ - (B-RED _j -B-OX ₂ ) _d -B-RED _j (Id),

wherein

OX ₂ , RED _j and B have the meaning given above, and

d represents an integer from 1 to 5,

contains.

8. Electrochromic system according to claims 1 to 7, characterized in that there is at least one electrochromic substance of the formulas (la) - (Id),

wherein

RED _{j stands} for the rest of the anodically reversibly oxidizable substance, which in the cyclic voltammogram, recorded in an inert solvent at room temperature, shows at least two chemically reversible oxidation waves, the first of these oxidation waves waves leads to an increase in absorbance at at least one wavelength in the visible range of the electromagnetic spectrum, and

B represents a pontic,

contains.

Electrochromic system according to Claims 1 to 8, characterized in that it contains at least one substance of the formula (Ia) - (Id), in which

OX ₂ for a rest of the formulas

2

2X ^'

2 X ^"

X ^"

R '°

I O

(VII),

N \

, 19th

stands, where

R ² to R ⁵ , R ⁸ , R ⁹ , R ¹⁶ to R ¹⁹ independently of one another C _j to C ₁₈ alkyl, C ₂ to C _j 2 alkenyl, C ₃ to C ₇ cycloalkyl, C ₇ to C ₁₅ aralkyl or C ₆ to C ₁₀ aryl or

R and R or R and R together form a - (CH ₂ ) ₂ - or - (CH ₂ ) ₃ bridge,

R ⁶ , R ⁷ and R ²² to R ²⁵ independently of one another are hydrogen, C _r to C ₄ alkyl, C _j to C ₄ alkoxy, halogen, cyano, nitro or C _j to C ₄ alkoxycarbonyl or R ²² and R ²³ and / or R ²⁴ and R ^{25 form} a -CH = CH-CH = CH bridge,

R ⁶⁹ to R ^{74 are} independently hydrogen or C _j -C ₆ alkyl, or

R ⁶⁹ ; R ¹² and / or R ⁷⁰ ; R ^{13 form} a -CH = H-CH = CH bridge,

R ^{26 is} hydrogen, C _j - to C ₄ -alkyl, C _j - to C ₄ -alkoxy, halogen, cyano,

Is nitro, C _j - to C ₄ -alkoxycarbonyl or C ₆ - to C ₁₀ -aryl,

1 0 1

E and E are independently O, S, NR or C (CH ₃ ) ₂ or

E ¹ and E ² together form an -N- (CH ₂ ) ₂ -N bridge,

R ^{1 is} C _j to C ₁₈ alkyl, C ₂ to C _j2 alkenyl, C ₄ to C ₇ cycloalkyl, C ₇ to C ₁₅ aralkyl, C ₆ to C ₁₀ aryl,

Z ^{1 is} a direct bond, -CH = CH-, -C (CH ₃ ) = CH-, -C (CN) = CH-, -CC1 = CC1-, -C (OH) = CH-, -CC1 = CH -, -C≡C-, -CH = NN = CH-,

Means -C (CH ₃ ) = NN = C (CH ₃ ) - or -CC1 = NN = CC1-,

Z ² - (CH ₂ ) _r - or -CH ₂ -C ₆ H ₄ -CH ₂ - means

r represents an integer from 1 to 10 and

X ^"represents an anion which is redox-inert under the conditions and which a) has a molar mass> 200 g / mol, preferably> 250 g / mol and / or b) has a cage-like structure, where the bond to the bridge member B is via one of the radicals R ² -R ¹⁹ , R ²² -R ²⁷ or, in the case where E ¹ or E ^{2 is} NR ^1, is via R ¹ and the radicals mentioned are then a direct bond,

RED _j for one of the following residues

6

(XVIII),

stands in what

R ²⁸ to R ³¹ , R ³⁴ , R ³⁵ , R ³⁸ , R ³⁹ , R ⁴⁶ , R ⁵³ and R ⁵⁴ independently of one another C _j - to C _j8 -alkyl, C ₂ - to C _j2 -alkenyl, C ₃ - bis C ₇ cycloalkyl, C ₇ to C ₁₅ aralkyl or C ₆ to C ₁₀ aryl, and R ⁴⁶ , R ⁵³ and R additionally denote hydrogen,

R ³² , R ³³ , R ³⁶ , R ³⁷ , R ⁴⁰ , R ⁴¹ , R ⁴² to R ⁴⁵ , R ⁴⁷ , R ⁴⁸ , R ⁴⁹ to R ⁵² and R ⁵⁵ to R independently of one another are hydrogen, C _j - to C ₄ -Alkyl, C _j - to C ₄ -alkoxy, halogen, cyano, nitro, C _j - to C ₄ -alkoxycarbonyl or

C ₆ - to C ₁₀ -aryl and R and R ⁵⁸ additionally represent an optionally benzanellated aromatic or quasi-aromatic five- or six-membered heterocyclic ring and R ⁴⁸ additionally denotes NR ⁷⁵ R ⁷⁶ ,

-CH = CH-CH = CH bridge,

Z ³ denotes a direct bond, a -CH = CH- or -N = N bridge,

= Z ⁴ = a direct double bond, a = CH-CH = or = ^: NN = bridge means

E ³ to E ⁵ , E ¹⁰ and E ¹¹ independently of one another denote O, S, NR ⁵⁹ or C (CH ₃ ) ₂ and E ⁵ additionally denotes C = O or SO ₂ , or

E ³ and E ⁴ independently of one another mean -CH = CH-,

E ⁶ to E ⁹ independently of one another are S, Se or NR ⁵⁹ ,

R ⁵⁹ , R ⁷⁵ and R ⁷⁶ independently of one another are C _j to C ₁₂ alkyl, C ₂ to C ₈ alkenyl, C ₃ to C ₇ cycloalkyl, C ₇ to C ₁₅ aralkyl or C ₆ to

C _j0 aryl and R ⁷⁵ additionally denotes hydrogen or

R ⁶¹ to R ⁶⁸ independently of one another are hydrogen, C _j - to C ₆ -alkyl, C _j - bis

C ₄ alkoxy, cyano, C _j to C ₄ alkoxycarbonyl or C ₆ to C ₁₀ aryl, or R ⁶¹ ; R ⁶² and R ⁶⁷ ; R ⁶⁸ independently of one another form a - (CH ₂ ) ₃ -, - (CH ₂ ) ₄ - or -CH = CH-CH = CH bridge,

v means an integer between 0 and 10,

the bond to the bridge member B via one of the radicals R ²⁸ -R ⁵⁸ , R ⁶¹ , R ⁶² , R ⁶⁷ , R ⁶⁸ or in the event that one of the radicals E ³ -E ^{π stands} for NR ⁵⁹

R ⁵⁹ takes place and the radicals mentioned then stand for a direct bond, and

B for a bridge member of the formulas - (CH ₂ ) _n - or

R ^{60 is} C _j to C ₆ alkyl, C ₂ to C ₆ alkenyl, C ₄ to C ₇ cycloalkyl, C ₇ to C ₁₅ aralkyl or C ₆ to C ₁₀ aryl,

n is an integer from 1 to 12,

m and p independently of one another are an integer from 0 to 8,

o is an integer from 0 to 6 and

q and s are independently 0 or 1,

and in the event that OX _{2 has} no positive charge, at least one

Conductive salt is contained, which contains the above-mentioned anion X ^" .

10. Electrochromic system according to claims 1 to 9, characterized in that it contains at least one substance of the formula (Ia) - (Id),

wherein OX _{2 represents} a radical of the formulas (II), (III), (IV) or (V),

in which

R ² , R ³ , R ⁴ , R ⁵ , R ⁸ and R ⁹ independently of one another for C _r to C ₁₂ alkyl, C ₂ to C ₈ alkenyl, C ₅ to C ₇ cycloalkyl, C ₇ to C, ₅ aralkyl or C ₆ - to C _j0 aryl,

R and R independently of one another represent hydrogen, methyl, ethyl, methoxy, ethoxy, fluorine, chlorine, bromine, cyano, nitro, methoxycarbonyl or ethoxycarbonyl,

R ¹⁰ , R ^π ; R ¹² , R ¹³ and R ¹⁴ , R ¹⁵ independently of one another for hydrogen or, if Z ^{1 is} a direct bond, in pairs in each case for a - (CH ₂ ) ₂ -, - (CH ₂ ) ₃ - or -CH = CH Bridge stand,

or

R ⁴ , R ⁵ and R ⁸ , R ^9, independently of one another, each in pairs together represent a - (CH ₂ ) ₂ - or - (CH ₂ ) ₃ bridge, if Z ¹ denotes a direct bond,

R ⁶⁹ to R ⁷⁴ are independently hydrogen or C _j -C ₄ alkyl,

R ¹ for C _j to C ₁₂ alkyl, C ₂ to C ₄ alkenyl, C ₅ to C ₇ cycloalkyl,

C ₇ to C ₁₅ aralkyl or C ₆ to C ₁₀ aryl,

Z ^{2 stands} for - (CH) _r - or -CH ₂ -C ₆ H ₄ -CH ₂ -,

r represents an integer between 1 and 6, X ^" for C ₁₀ to C ₂₅ alkanesulfonate, preferably C ₁₃ to C ₂₅ alkanesulfonate, C ₃ to C ₁₈ perfluoroalkanesulfonate, preferably C ₅ to C _j8 perfluoroalkanesulfonate, C ₁₃ to C ₂₅ alkanoate, benzenesulfonate substituted by nitro, C ₄ - to C ₂₅ -alkyl, perfluoro-C _j - to C ₈ -alkyl, C _j - to C ₁₂ -alkoxycarbonyl or dichloro, optionally by nitro, cyano, hydroxy, C _j - to C ₂₅ -Alkyl, C _j - to C _{] 2} -alkoxy, amino, C _j - to C ₁₂ -alkoxycarbonyl or chlorine-substituted naphthalene or biphenyl sulfonate, optionally substituted by nitro, cyano, hydroxy, C _j - to C ₂₅ -alkyl, C _j - Substituted to C ₁₂ alkoxy, C _j to C ₁₂ alkoxycarbonyl or chlorine

Benzene, naphthalene or biphenyl disulfonate, benzoate substituted by dinitro, C ₆ to C ₂₅ alkyl, C ₄ to C ₁₂ alkoxycarbonyl, benzoyl, chlorobenzoyl or toluoyl, the anion of naphthalenedicarboxylic acid, diphenyl ether disulfonate, tetraphenyl borate phenylborate, tetra-C ₃ - to C ₂₀ -alkoxyborate, tetraphenoxyborate, 7,8- or 7,9-dicarba-nido-undecaborate (1-) or (2-), which may be attached to the B- and / or C- Atoms are substituted by one or two C _j - to C ₁₂ - alkyl or phenyl groups, dodecahydrodicarbadodecaborate (2-) or BC _j - to C ₁₂ alkyl-C-phenyl-dodeca- hydrodicarbadodecaborate (l-), where polyvalent anions such as naphthalene disulfonate X ^" stand for one equivalent of this anion,

where the bond to the bridge member B is via one of the radicals R ² -R or, in the case where E ¹ or E ^{2 is} NR ^1, is via R ¹ and the radicals mentioned are then a direct bond,

RED _j for a radical of the formulas (X), (XI), (XII), (XIH), (XVI), (XVII),

(XViπ) or (XX) stands,

in which

R ²⁸ to R ³¹ , R ³⁴ , R ³⁵ , R ³⁸ , R ³⁹ , R ⁴⁶ , R ⁵³ and R ⁵⁴ independently of one another C _j - to C ₁₂ -alkyl, C ₂ - to C ₈ -alkenyl, C ₅ - bis C ₇ cycloalkyl, C ₇ to C ₁₅ aralkyl or C ₆ to C _{] 0} aryl and

R ⁴⁶ , R ⁵³ and R ⁵⁴ additionally denote hydrogen, R ³² , R ³³ , R ³⁶ , R ³⁷ , R ⁴⁰ , R ⁴¹ , R ⁴⁷ to R ⁵² , R ⁵⁵ and R ⁵⁶ independently of one another hydrogen, methyl, ethyl, methoxy, ethoxy, fluorine, chlorine, bromine, cyan, nitro , Methoxycarbonyl, ethoxycarbonyl or phenyl and

R ⁵⁷ and R ⁵⁸ additionally denote 2- or 4-pyridyl and

R ⁴⁸ additionally means NR ⁷⁵ R ⁷⁶ ,

Z ³ denotes a direct bond, a -CH = CH- or -N = NB backbone,

= Z ⁴ = a direct double bond, which means = CH-CH = or = NN = bridge,

E ⁶ to E ⁹ are identical to one another and denote S, Se or NR ⁵⁹ and

E ⁵ additionally means C = O,

E ^{6 stands} for NR ⁵⁹ , where R ^{59 means} a direct bond to bridge B and

^* 7 O

E to E have the meaning given above, but need not be identical to one another,

R ⁷⁵ and R ⁷⁶ in the meaning of NR ⁷⁵ R ⁷⁶ together with the N atom to which they are attached mean pyrrolidino, piperidino or morpholino, R ⁶¹ , R ⁶² and R ⁶⁷ , R ⁶⁸ independently of one another for hydrogen, C _r to C ₄ - alkyl, methoxycarbonyl, ethoxycarbonyl or phenyl or in pairs together for a - (CH ₂ ) ₃ - or - (CH ₂ ) ₄ -B stand back,

R ⁶³ to R ⁶⁶ stand for hydrogen and

v represents an integer from 1 to 6,

wherein the bond to the bridge member B via one of the radicals R ²⁸ -R ⁴¹ , R ⁴⁶ -R ⁵⁶ , R ⁶¹ , R ⁶² , R ⁶⁷ , R ⁶⁸ or in the event that one of the radicals E ³ -E ^{H is} NR ⁵⁹ , takes place via R ⁵⁹ and the radicals mentioned then stand for a direct bond,

- (CH) _m -NR ⁶⁰ - (CH ₂ ) _p -, - (CH ₂ ) _m -C ₆ H ₄ - (CH ₂ ) _p -, - [O- (CH ₂ ) _p ] ₀ -O-, - [NR ⁶⁰ - (CH ₂ ) _p ] _o -NR ⁶⁰ -, - [C ₆ H ₄ - (CH ₂ ) _p ] _o -C ₆ H ₄ -, - (CH ₂ ) _m -OCO-C ₆ H ₄ -COO- (CH ₂ ) _p -, - (CH ₂ ) _m -NHCO-C ₆ H ₄ -CONH- (CH ₂ ) _p -, - (CH ₂ ) _m -NHCONH-C ₆ H ₄ -NHCONH- (CH ₂ ) _p -,

R ^{60 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.

11. Electrochromic system according to claims 1 to 10, characterized in that it contains at least one substance of the formula (Ia) - (Id),

wherein OX _{2 represents} a radical of the formulas (II), (IV) or (V),

in which

0 Δ δ

R, R and R stand for a direct bond to the bridge member B,

R, R and R independently of one another represent methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, benzyl or phenyl, or

R, R and R in the case of the formulas Ic and Id also stand for a direct bond to the bridge member B,

R ⁶ and R ^{7 are the} same and represent hydrogen, methyl, methoxy, chlorine, cyano or methoxy carbonyl,

R to R are identical and denote hydrogen, methyl or ethyl,

R ⁷³ and R ^{74 are} hydrogen,

E ¹ and E ^{2 are the} same and stand for O or S,

Z ^{1 stands} for a direct bond or -CH = CH-,

X ^" for C ₁₅ - to C ₂₂ alkanesulfonate, C ₈ - to C ₁₂ perfluoroalkanesulfonate, nitrobenzenesulfonate, dinitrobenzenesulfonate, mono- or bis-C ₄ - to C ₁₂ -alkylbenzenesulfonate, dichlorobenzenesulfonate, naphthalenesulfonate, nitronaphthalenonaphthalate, or nitronaphthalenesulfonate To-

C ₃ - -alkylnaphthalinsulfonat to _{C] 2,} Hydroxynaphthalinsulfonat, benzenedisulfonate Aminonaphthalinsulfonat, biphenyl disulphonate, benzenedisulfonate, nitro, C ₄ - to C ₁₂ -Alkylbenzoldisulfonat, naphthalene, Nitronaphthalindisulfonat, C ₄ - to C ₁₂ -Alkylnaphthalindi- sulfonate, Biphenyldisulfonat, dinitrobenzoate, Mono- or bis-C ₈ to C ₁₂ alkyl benzoate, C ₆ to C _{] 2} alkoxycarbonyl benzoate, benzyl benzoate, toluoyl benzoate, the anion of naphthalenedicarboxylic acid, cyanotriphenylborate, tetra-C ₄ _{-C 12} -alkoxyborate, tetraphenoxyborate, 7,8- or 7,9-dicarba-nido-undecaborate (l-) or (2-), which are optionally substituted on the B and / or C atoms by one or two methyl, ethyl, butyl or phenyl groups, do- decahydrodicarbadodecaborate (2-) or B-methyl-C-phenyl-dodeca- hydro dicarbadodecaborate (1-), with polyvalent anions such as naphthalene disulfonate X ^{"representing} an equivalent of this anion,

RED represents a radical of the formulas (X), (XII), (XIII), (XVI) or (XVII),

R ²⁹ to R ³¹ , R ³⁵ and R ³⁹ independently of one another represent methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, benzyl or phenyl, or

R ³⁰ , R ³⁵ and R ³⁹ in the case of the formulas Ib and Ic also stand for a direct bond to the bridge member B,

R ³² , R ⁴⁷ and R ^{48 represent} hydrogen,

R ³⁶ , R ³⁷ , R ⁴⁰ , R ⁴¹ and R ⁵⁰ to R ⁵² independently of one another represent hydrogen, methyl, methoxy, chlorine, cyano, methoxycarbonyl or phenyl, or

R ⁵¹ in the case of the formulas Ib and Id also stands for a direct bond to the bridge member B,

Z ^{3 stands} for a direct bond, a -CH = CH- or -N = N bridge,

= Z ⁴ = stands for a direct double bond, a = CH-CH = or = NN = bridge, E ³ to E ⁵ independently of one another represent O, S or NR ⁵⁹ , but E ³ and E ⁴ have the same meaning,

E ⁶ to E ⁹ are identical to one another and stand for S, Se or NR ⁵⁹ ,

R ^{59 represents} methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, benzyl or phenyl, or

R ⁵⁹ in the case of the formula XVI in the formula Ib and Id also represents a direct bond to the bridge member B,

- (CH ₂ ) _m -NR ⁶⁰ - (CH ₂ ) _p -, - (CH ₂ ) _m -C ₆ H ₄ - (CH ₂ ) _p -, -O- (CH ₂ ) _p -O-, -NR ⁶⁰ - (CH ₂ ) _p -NR ⁶⁰ -,

- (CH ₂ ) _m -OCO-C ₆ H ₄ -COO- (CH ₂ ) _p -,

- (CH ₂ ) _m -NHCO-C ₆ H ₄ -CONH- (CH ₂ ) _p -,

- (CH ₂ ) _m -NHCONH-C ₆ H ₄ -NHCONH- (CH ₂ ) _p -,

- (CH ₂ ) _m -OCO- (CH ₂ ) _t -COO- (CH ₂ ) _p -, - (CH ₂ ) _m -NHCO- (CH ₂ ) _t -CONH- (CH ₂ ) _p -,

- (CH ₂ ) _m -NHCONH- (CH ₂ ) _t -NHCONH- (CH ₂ ) _p -,

R ^{60 represents} methyl,

n represents an integer from 1 to 10,

m and p are the same and represent an integer from 0 to 2 and

t represents an integer from 1 to 6.

12. Electrochromic system according to claims 1 to 11, characterized in that it has at least one electrochromic substance of the formula (Ia)

OX ₂ -B-RED _j (la)

according to one of the formulas

(XXV),

(XXVII),

(XXVIII),

X

(XXIX), or

(XXXIV),

or at least one substance of the formula (Ic) according to one of the formulas

(XXXVTI),

(XXXVIII),

(XXXIX),

(XL),

(XLI)

(XLΠ) contains, in which

R ⁶ , R ⁷ and R ³⁶ , R ³⁷ are identical in pairs and represent hydrogen, methyl, methoxy, chlorine, cyano or methoxycarbonyl,

R ¹² and R ^{13 represent} hydrogen or, if Z ¹ denotes a direct bond, together represent a CH = CH bridge,

R ⁶⁹ to R ^{72 are the} same and represent hydrogen or methyl,

E ¹ and E ^{2 are the} same and stand for O or S, Z ^{1 represents} a direct bond or -CH = CH,

R ³² , R ⁴⁷ and R ^{48 represent} hydrogen,

E ³ to E ⁵ independently of one another represent O, S or NR ⁵⁹ , but E ³ and E are the same,

R to R and R independently of one another are methyl, ethyl, propyl,

Butyl, pentyl, hexyl or benzyl, where R ²⁹ to R ^{31 are} preferably the same,

Z ^{3 represents} a direct bond, -CH = CH- or -N = N-,

E ⁶ to E ⁹ are identical to one another and stand for S, Se or NR ⁵⁹ ,

Z ^{4 stands} for a direct double bond, a = CH-CH = or = NN = bridge,

m represents an integer from 1 to 5,

u stands for 0 or 1 and

X ^" for C ₁₅ - to C ₂₀ alkanesulfonate, C ₅ - to C ₈ perfluoroalkanesulfonate, mono- or dibutylbenzenesulfonate, mono- or di-tert-butyl-benzenesulfonate, octylbenzenesulfonate, dodecylbenzenesulfonate, naphthalenesulfonate sulfonate, biphenylbenzene sulfonate, biphenyl sulfonate, biphenyl sulfonate, biphenyl sulfonate, biphenyl sulfonate Naphthalenedisulfonate, dibutylnaphthalenesulfonate, biphenyldisulfonate, benzoylbenzoate, cyanotriphenylborate, tetra-C ₃ - to C ₈ -alkoxyborate, tetraphenoxyborate, 7,8- or 7,9-dicarba-nido-undecaborate (l-) or

(2-) or dodecahydro-dicarbadodecaborate (2-) is, with polyvalent anions such as naphthalene disulfonate X ^"stands for an equivalent of this anion.

13. Electrochromic substance according to the formula

Y-KB-Z ^ B-Y ^ B-Z (I),

wherein

Y and Z independently of one another represent a radical OX ₂ or RED _j , but at least one Y represents OX ₂ and at least one Z represents RED _j , where OX _{2 represents} the rest of a reversibly electrochemically reducible cationic redox system which acts as a counterion Anion X ^" according to claim 1, and RED _{j stands} for the rest of a reversibly electrochemically oxidizable redox system.

14. Electrochromic liquid containing an electrochromic system according to at least one of claims 1 to 12 and at least one inert solvent.

15. Electrochromic device containing an electrochromic liquid according to claim 14.

16. Electrochromic device according to claim 15, characterized in that it is a cell such as e.g. a solar cell is designed as a window pane, mirror, sunroof or display.

17. Electrochromic device according to claims 15 and 16, characterized in that it consists of two mutually facing translucent glass or plastic panes, one of which is optionally mirrored and whose mutually facing sides are coated in an electrically conductive manner between which the electrochromic liquid is contained.