MXPA00001682A - Electrochromic device with improved lightfastness - Google Patents

Abstract

5-Aryl-10-alk(en)yl, -cycloalkyl- and -aralkyl-dihydrophenazines and bridged bis(10-alk(en)yl, -cycloalkyl- and -aralkyl-dihydrophenazin-5-yls) are new. Dihydrophenazines of formula (IA) are new;A-R<201>(IA) A=a dihydrophenazin-5-yl group of formula (A-1);R<201>=6-10C aryl;R<202>=2-12C alk(en)yl, 3-7C cycloalkyl or 7-16C aralkyl;R<203>, R<204>=hydrogen (H), halogen, 1-4C alkyl, 1-4C alkoxy, cyano (CN) or 6-10 C aryl;m, n=1-4;or 2 adjacent R<203>and R<204>groups=a divalent -CH=CH-CH=CH- group if m and/or n=2. Independent claims are also included for:(a) new bridged bisdihydrophenazin-5-yls of formula (IB);(b) an electrochromic medium containing a pair of electrochromic substances OX2 and RED1, in which RED1 is a dihydrophenazine or dihydroquinoxaline of formula (IA) or a bridged bisdihydrophenazin-5-yl or bisdihydroquinoxalin-1-yl of formula (IB) with a wider range of substituents. A-B-A (IB) A=a dihydrophenazin-5-yl group of formula (A-1);R<202>=1-12C alkyl, 3-7C cycloalkyl, 2-12C alkenyl, 7-16 C aralkyl or 6-10 C aryl;B=-(CH2)p-, CH2, -(O-CH2)q-O-CH2 or -(CH2)r-C6H4-(CH2)s-, in which the CH2 groups may be substituted by methyl;p=2-20;q, r, s=0-10;R<203>, R<204>=H, halogen, 1-4C alkyl, 1-4C alkoxy, CN or 6-10C aryl;a divalent -CH=CH-CH=CH- group if m and/or n=2. m, n=1-4.

Description

ELECTROCROMIC DEVICE WITH LIGHT SOLIDITY IMPROVED. Field of the invention. The present invention relates to an electrochromic device with improved light fastness. Description of the prior art. Electrochromic devices are already known, for example by D. Theis in Ullmann's Encyclopedia of Industrial Chemistry, Vol. A 8, page 622, Verlag Chemie 1987 and WO-A 94/23333. A distinction is made between two basic types: Type 1: total surface electrochromic device. Type 2: electrochromic signaling device with structured electrodes. Type 1 finds application, for example, in electrically obscured window panes or in mirrors for electrically dimpable cars. Such devices are known, for example, from US-A 4 902 108. Type 2 finds application in the segment and matrix markers.

Such signaling devices have been proposed, for example, in DE-A 196 31 728. Such devices can be observed by transmission or by reflection in case they are damaged. WO-A 94/23333 compares electrochromic materials with different construction, but which have not been used as signaling devices: Construction a: The electrochromic substances are in the form of a film or a solid layer on the electrodes (Ullmann, cf. higher). Construction b: Electrochromic substances are deposited as a layer on the electrodes during the redox process (Ullmann, see REF. : 32551 above). Construction c): Electrochromic substances always remain in solution. The most known electrochromic material for construction a) is the tungsten oxide pair palladium hydride. For the construction b) viologens have been described as electrochromic substances. These devices are not self-extinguishing, therefore the image generated after the disconnection of the current remains and can only be erased again by inverting the poles of the voltage. Such devices are not particularly stable and do not allow a large number of connection cycles. Furthermore, those cells, especially made of tungsten oxide / palladium hydride, can not be made to work with light transmission but only by reflection due to the scattering of the light on these electrochromic layers. It is known from the publications Elektrokhimiya 13, 32-37 (1977); 13, 404-408, 14, 319-322 (1978), US-A 4 902 108 and US-A 5 140 455 an electrochromic system with this construction c) cited last. In an electrochromic cell, which is constructed from conductively coated glass plates, a solution of a pair of electrochromic substances in an inert solvent is contained. As a pair of electrochromic substances, respectively, an electrochromic substance, reversibly reducible and an electrochromic substance, reversibly oxidizable, is used. Both are colorless in basic state or are only weakly colored. Under the effect of an electrical voltage it is - > - reduces one of the substances, the other is oxidized, with which both are colored. After disconnection of the tension, the two substances are again formed in the base state, with which the decolourised or the color rinse is present.

RED, + OX RED, * «4- ± OX, + (colorless) (colored) (low energy pair) (high energy pair) It is known from US-A 4 902 108 that those pairs of redox substances are suitable wherein the reducible substance has at least two chemically reversible reduction thresholds in the cyclic voltammogram and the oxidizable substance has correspondingly at least two chemically reversible oxidation thresholds. According to WO-A 94/23333 such solvent systems of construction C have, however, serious drawbacks. The diffusion of the electrochromic substances in the solution causes diffuse limits of the colors and causes a high current consumption for the maintenance of the colored state since the colored substances are permanently degraded by recombination and reaction on the opposing electrodes respectively. However, various applications for such electrochromic cells have been described with construction c). In this way they can be configured, for example, as a rear-view mirror for cars, which darkens during night driving by applying a tension and, thus, prevent blindness due to the headlights of the vehicles located at the rear (US-A). 3 280 701, US-A 4 902 108, EP-A 0 435 689). In addition, such cells can also be used as windows for windows or self-insulating ceilings. that obscure sunlight after application of a voltage. In the same way, the application of such devices as electrochromic signaling devices has been described, for example in segment or matrix signaling devices with structured electrodes (DE-A 196 31 728). Electrochromic cells are usually constituted by a pair of glass plates, one of which is specular in the case of self-reflection. The side of these plates is surface-coated with a light-permeable, electrically conductive layer, for example indium tin oxide (ITO), this conductive coating being subdivided, in the case of signaling devices, into segments electrically separated from each other. Yes, they contact each other individually. From this plate, a cell is now constructed by joining with its coated sides electrically conductive, directed to each other, by means of a joint ring to give a cell. In . this cell is now charged with an electrochromic liquid through an opening and the cell is hermetically sealed. The two plates are connected to a voltage source through the ITO layers. The electrochromic devices described above show, as a rule, a sensitivity to light, especially against UV light. Therefore, for example, in US-A 5 280 380, electrochromic devices containing UV absorbers have been described. In contrast to the use of UV absorbers, it would be advantageous to use electrochromic compounds that inherently have improved light stability.

- - Detailed description of the invention. Surprisingly it has now been found that the use of certain dihydronaphthazines or dihydrophenazines leads to improved light stability of electrochromic devices. Thus the object of the invention is an electrochromic device containing a pair of glass or plastic plates or sheets of synthetic material, between whose plates or sheets at least one, preferably both plates or sheets are provided respectively on one side with an electrically conductive coating, between whose plates or sheets at least one, and its conductive coating, are transparent, the other may be mirror-like and between which at least in one of the two plates or sheets the electrically conductive layer can be subdivided into segments separate surfaces, individually contacted, the plates or sheets being joined by means of a joint ring on the side of their conductive coating, and the volume, formed by the two plates or sheets and by the joint ring is filled with an electrochromic medium , which contains a pair of electrochromic substances OX2 and REDi, characterized in that REDi corresponds to na of the formulas (CCIII) wherein R201 means aryl, R202 means alkyl, cycloalkyl, alkenyl, aralkyl or aryl, B means a bivalent bridge, R203 to R206 independently of one another, meaning hydrogen, halogen, alkyl, alkoxy, cyano or aryl, m and n independently of each other mean an integer from 1 to 4 or two contiguous R203 and R204, independently of each other, mean a bivalent moiety -CH = CH-CH = CH-, when either n means > 2.

Such dihydrophenazipase are known, for example, from H. Gilman and J.J Dietrich, J. Amer. Chem. Soc. 79 (1957) 6178 or can be obtained analogously. Preferred dihydronaphthazines and dihydrophenazines of the formulas (CC) to (CCIII) are those in which R201 means aryl with 6 to 10 carbon atoms, R202 means alkyl with 1 to 12 carbon atoms, cycloalkyl with 3 to 7 atoms carbon, alkenyl with 2 to 12 carbon atoms, aralkyl with 7 to 16 carbon atoms or aryl with 6 to 10 carbon atoms, B means - (CH -.) P-, - (CH2) - (O-CH2) q-OCH2- or - (CH2) r-C6H4- (CH2) s-, where the CH2- group can be substituted by methyl, R203 to R206 independently of one another, they mean hydrogen, halogen, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms carbon, cyano or aryl with 6 to 10 carbon atoms, m and n independently of each other, mean an integer from 1 to 4 or two R203 and R2 (M contiguous, independently of each other, mean a bivalent radical -CH = CH-CH = CH-, when m or n means > 2, p means an integer from 2 to 20 and q, r and s independently from one another, mean an integer from 0 to 10. Especially preferred dihydronaphthazines and dihydrophenazines of the formulas (CC) to (CCIII) are those in which, R201 means phenyl, which can optionally carry up to three methyl, methoxy, chloro, bromo or cyano radicals, R20: means alkyl having from 1 to 8 carbon atoms, if appropriate branched, cyclopentyl, cyclohexyl, benzyl, phenethyl, phenylpropyl or phenyl these residues can, if appropriate, carry up to three methyl, methoxy, chloro, bromo or cyano radicals, B means - (CH2) P-, R203 to R206 independently of one another, meaning hydrogen, chlorine, bromine, methyl, ethyl, propyl, butyl, methoxy, ethoxy, cyano or phenyl, m and n independently of each other, mean an integer from 1 to 2, or two contiguous R203 and R204, independently of each other, mean a bivalent moiety -CH = CH-CH = CH-, when how well n means 2 and p means an integer from 2 to 10. In a very particularly preferred manner, the electrochromic device according to the invention contains a REDi of the formula (CC). Preference is given to those dihydrophenazines of the formula (CC)wherein R201 means phenyl, R202 means methyl, ethyl, propyl, butyl, phenylpropyl or phenyl, particularly preferably phenyl, R203 and R204 means hydrogen and m and n mean 1. Also very preferably the electrochromic device according to the invention contains a REDi of the formula (COI). Preferred are dihydrophenazines of the formula (COI), in which R202 means phenyl, B means - (CH? Y, R203 and R204 mean hydrogen, m and n mean 1 and p means an integer from 2 to 6. The electrochromic device according to invention contains, in addition to the REDi electrochromic substances of the formulas (CC) up to (COII) at least one OX2 electrochromic substance, but it can also contain other REDi by selecting the REDi and OX2 electrochromic compounds and / or mixtures thereof monochromatic color shades of any type can be established For a polychromatic color representation, two or more electrochromic devices of this type can be arranged in a stacked manner, each of these devices being able to generate a different color tonality. this type in such a way that the devices that are in physical contact have in c or a light-permeable plate, which is then covered in a conductive manner on both sides and subdivided into segments respectively according to the embodiment. By way of example, a stack consisting of three electrochromic devices is then formed by at least four plates. By means of the connection of the segments in these various stacked devices, markings with various colors can be made. If the segments placed in series of the various devices of this type are connected, mixed colors will be obtained. In this way arbitrary colors can be represented in the context of a trichromy, ie for example color images. Preferred are those electrochromic devices according to the invention which contain an oxidizable substance REDi of the formulas (CC) up to (COII) as well as an OX2 reducible substance as well as, if appropriate, other oxidizable and / or reducible substances, where a) the reducible substance has at least one reduction threshold, preferably at least two chemically revble reduction thresholds in the cyclic voltammogram and the oxidizable substance has correspondingly at least one oxidation threshold, preferably at least two chemically revble oxidation thresholds, or b) the reducible substance and the oxidizable substance are covalently bonded together via a bridge B, or c) are selected as a reducible substance and / or as an oxidizable substance those in which the revble transition between the oxidizable form and the reducible form or the rev is related with the break or with the formation of a link s-, od) the subs reducible substance and / or the oxidizable substance are metallic salts or metal complexes of those metals that exist at least in two oxidation levels, or e) the reducible and / or oxidizable substance are oligomand polym which contain at least one of the redox systems cited, as well as pairs of such redox systems, such as those defined in a) to d), or as a reducible and / or oxidizable substance, mixtures of the substances described in a) to e) are used. In the sense of the invention, the appropriate OX2 and the other REDi are those substances which provide RED2 and OXi products during their reduction or oxidation on the cathode or the anode in the aforementioned solvent, which do not enter into a subsequent chemical reaction, but they can be oxidized or reduced again to give OX2 and REDi. The suitable reducible OX2 substances are. for example, 4X- 2X- 2 X-, 16 -CH._ (VI). 17 X- twenty R1 where R2 to R5. R8, R9, R16 to R19 means alkyl with 1 to 18 carbon atoms, alkenyl with 2 to 12 carbon atoms, cycloalkyl with 4 to 7 carbon atoms, aralkyl with 7 to 15 carbon atoms or aryl with 6 to 10 atoms carbon or R4; R5 or R8; R9 can jointly form a bridge - (Ohb- or - (CH2 -, R6, R7 and R22 to R25, independently of each other, mean hydrogen, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, halogen , cyano, nitro or alkoxycarbonyl with 1 to 4 carbon atoms or R22, R23 and / or R24; R25 can form a bridge -CH = CH-CH = CH-, R '; R ", R10; R13, R12; R13 and R'4; R15 independently of each other, means hydrogen or in a paired manner means a bridge - (22) 2-, - (CH2) 3- or -CH = CH-, R20 and R21 independently of each other, mean O, N-CN, C (CN) 2 or N-aryl with 6 to 10 carbon atoms, R26 and R27 mean hydrogen, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, halogen, cyano, nitro , alkoxycarbonyl with 1 to 4 carbon atoms or aryl with 6 to 10 carbon atoms R69 to R74, R80 and R81 independently of one another, mean hydrogen or alkyl having 1 to 6 carbon atoms or R69, R12, R70, R, 3, R73, R80 and / or R74, R8 'together form a bridge -CH = CH-CH = CH-, E1 and E2 independently of each other, mean O, S, NR1 or C (CH3) 2 or E1 and E2 together form a bridge -N- (CH2) 2-N, R1 means alkyl with 1 to 18 carbon atoms, alkenyl with 2 to 12 carbon atoms, cycloalkyl with 4 to 7 carbon atoms, aralkyl with 7 to 15 carbon atoms, aryl with 6 to 10 carbon atoms. Z1 means a direct bond, -CH = CH-, -C (CH3) = CH-, -C (CN) = CH-, CC1 = CC1-, -C (OH) = CH-, -CC1 = CH-, -C = C-, -CH = NN = CH-, C (CH3) = NN = C (CH3) - or -CC1 = NN = CC1-, Z2 means - < CH2) r- or -CE2-C ^ -CE2-, r means an integer from 12 to 10, R94 and R95 independently of one another, meaning hydrogen or cyano, R101 to R105 independently of each other, mean aryl with 6 to 10 atoms of carbon or a heterocyclic ring with 5 or 6 members, aromatic or almost aromatic, optionally benzo-ring, R107, R109, R113 and R114 independently of each other, means a residue of the formulas (CV) up to (CVH) R i 5 R R i? R i in in inertly to each other, means aryl having 6 to 10 carbon atoms or a residue of the formula (CV), Rn0 to R112, R "7 and R118 independently of one another, mean hydrogen, alkyl with 1 to 4 carbon atoms, halogen or cyano, E101 and E102 independently of each other mean O, S or NR "9, R1'9 and R122 independently of each other, mean alkyl with 1 to 18 carbon atoms, alkenyl with 2 to 8 carbon atoms, cycloalkyl with 4 to 7 carbon atoms, aralkyl with 7 to 15 carbon atoms or aryl with 6 to 10 carbon atoms, R'06, R120, R121, R123 and R124 independently of each other, mean hydrogen, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, halogen, cyano, nitro or alkoxycarbonyl with 1 to 4 carbon atoms or R120, R121 or R123, R124 together form a bridge -CH = CH- CH = CH-, A1, A2 and A3 independently of each other mean O or C (CN) ?, R 96 means hydrogen, phenyl or tere. -butyl and X "means an inert anion under the redox conditions.The suitable oxidizable REDi substances are, for example (XXI), (XXIII), (XXVII),, 53 Mía R56 (XXVIII),, 54 (XXXII), (XXXIII), wherein R28 to R31, R34, R33, R38, R39, R46, R33 and R54 independently of each other mean alkyl with 1 to 18 carbon atoms, alkenyl with 2 to 12 carbon atoms, cycloalkyl with 4 to 7 carbon atoms, aralkyl with 7 to 15 carbon atoms or aryl with 6 to 10 carbon atoms, R32, R33, R36, R37, R40, R442 to R4i, R47, R48, R49 to R3: and R55 to R58 independently of one another, meaning hydrogen, alkyl having 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, halogen, cyano, nitro, alkoxycarbonyl with 1 to 4 carbon atoms, aryl with 6 to 10 carbon atoms carbon and R57 and R58 also mean a heterocyclic ring, of 5 or 6 members, aromatic or quasi aromatic, which optionally is benzo-ring and R48 means ade¬ more NR75R76, or R49; R50 and / or R51; R32 form a bridge - (Ofc) .-, - (Ofc - (Oh) .- or -CH = CH-CH = CH-, Z3 means a direct bond, a bridge -CH = CH- or -N = N, = Z4 = means a direct double bond, a bridge = CH-CH = or = NN =, E3 to E5, E10 and E "independently of each other, mean O, S, NR39 or C (CH3) 2 and E5 also means C = O or SO2, E3 and E4 independently of each other, can also mean -CH = CH-, E6 to E9 stand for, independently of each other, S, Se or NR59, R39, R73 and R76 independently of one another, meaning alkyl with 1 to 12 carbon atoms, alkenyl with 2 to 8 carbon atoms, cycloalkyl with 2 to 7 carbon atoms. carbon, aralkyl with 7 to 15 carbon atoms, aryl with 6 to 10 carbon atoms.

R73 further denotes hydrogen or R73 and R76 mean, in the meaning of NR7ÍR76 with the N atom, with which they are linked, a ring with five or six members containing, if appropriate, other heteroatoms, R61 to R68 mean, independently of each other , hydrogen, alkyl having 1 to 6 carbon atoms, alkoxy with 1 to 4 carbon atoms, cyano, alkoxycarbonyl with 1 to 4 carbon atoms or aryl with 6 to 10 carbon atoms and R61; R62 and R67; R68 independently of each other, they also form a bridge - (0.2) 3-, - (OÍ2) 4-o -CH = CH-CH = CH- or R62 R63 and R64 R65 and R66 R67 form a gate _0-CH2CH2-O- OR v means an integer between 0 and 100, R82, R83, R88 and R89 independently of one another, meaning alkyl with 1 to 18 carbon atoms, alkenyl with 2 to 12 carbon atoms, cycloalkyl with 4 to 7 carbon atoms, aralkyl with 7 to 15 carbon atoms or aryl with 6 to 10 carbon atoms, R84 to R87 and R90 to R93 mean, independently of one another, hydrogen or alkyl having 1 to 6 carbon atoms or R84 R86 > R_5 R87) R9o R 2 and / or R! R93 fopnan conjunctly a bridge -CH = CH-CH = CH-.

Also suitable as redi are anions such as, for example, redox systems, linked through a bridge B, in the case of oligomers or polymers, for example those of the formula Y - [- (- BZ -), - ( -BY-Hc-BZ (L), in which Y and Z signify, independently of each other, a rest OX2 or REDi, however meaning a Y at least OX2 and Z at least REDi or Y and Z mean OX2, where OX2 means the rest of a reversible redox system, electrochemically reducible and REDi means a remnant of a reversible redox system, electrochemically oxy¬ possible, B means a bridge member, c means an integer from 0 to 1,000, and a and b mean, independently of each other, an integer from 0 to 100. Preferably (a + b) -c < 10,000.

In this case it is desired to be indicated by reducible or electrochemically, reversible oxidizable, that the transfer of the electrons can be verified without or with modification of the structure s completely within the meaning of the aforementioned definition of the OX2 and REDi according to the invention. In particular, they are to be indicated by means of the electrochemical compounds of the formula (L) those of the formulas OX2-B-RED.-B-OX2 (Lb), RED1-B-OX2B-RED1 (Le), OX2- (B-RED .-B-OX2) -B-RED. (Ld) or OX2- (B-OX2) .- B-OX2 (Le) where OX2, REDi and B have the meaning indicated above, d means an integer from 1 to 5 and e means an integer from 0 to 5. In the formulas (L) and (La) up to (Le) it is indicated with OX2 and REDi especially residues of the redox systems described above of the formulas up to (X), (Cl) to (CIV) and (XX) to (XXXIII ), carrying out the link with the bridge member B through one of the remains R2 to R19, R22 to R27, R28 to R38, R6 to R62, R67, R68, R83, R88, R122 or, in the case where one of the residues E1 or E2 means NR 'or one of residues E3 to E "means NR39 or one of the residues E101 to E102 means NR "9, through R \ R39 or R" 9 and the above moieties mean a direct link, and B means a bridge of the formulas - (CH) n- or - [Yls (CH2) m-Y2] o- (CH2) p-Y3q-, which may be substituted by alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, halogen or phenyl, Y1 to Y3 mean, independently of each other, O, S, NR60, COO, CONH, NHCONH, cyclopentanediyl, cyclohexanediyl, phenylene or naphthylene, R60 means alkyl with 1 to 6 carbon atoms, alkenyl with 2 to 6 carbon atoms, cycloalkyl with 4 to 7 carbon atoms, aralkyl with 7 to 15 carbon atoms or aryl with 6 to 10 carbon atoms, n means an integer from 1 to 12, and p and p mean, independently of each other, an integer from 0 to 8. , or means an integer from 0 to 6 and q and y mean, independently of each other, 0 or 1. They are particularly preferred to be indicated with OX: and REDi in the formulas (L) and (La) to (Le) remains of the systems previously described redox of the formulas (I), (V), (XX), (XXII), (XVIII), (XXV), (XXVI) and (XXXIII). In another type of oligomeric or polymeric systems, the OX2 and / or REDi groupings can also be linked, for example, in the form of side chains on a main group, for example a poly (meth) acrylate, silicone, polycarbonate, polyurethane, polyurea, polyester. , polyamide, cellulose or on other oligomer systems or polymers. Examples of metal salts or metal complexes, which can be used as OX2 or REDi are Fe3 + 2+, Ni3 + 2+, Co3 + 2+, Cu2 + +, [Co (CN) 6] 3"'4", [Fe (cyclopentadienyl) 2] 0 / +, Lu (PC) 2+ has, a 2- (Pe = phthalocyanine), Fe [Fe (CN) 6] 0 / l. "As counterions of metal ions and cationic complexes all the redox-inert anions X 'are considered, as will be described in more detail below, by way of counterions of the anionic complexes, all the redox-inert M + cations, for example alkali metals or quaternary ammonium salts, such as Na +, K +, N (CH3) 4+, NÍQHÜV, C6HJCH2N (CH3) 3+ and others Also preferred is an electrochromic device containing mixtures of the aforementioned electrochromic substances generally and preferably. (I) + (O) + (CC), (I) + (IV) + (CC) + (XXII), (La) + (I) + (CC) + (XXVI), without this being expressed no type of delimitation The proportions in the mixture can vary within wide limits.

These allow the optimization of a desired shade of color or degrees of gray and / or the optimization of the desired dynamics of the device. In the meanings of the aforementioned substituents, the alkyl radicals, even in the modified state, for example the alkoxy or aralkyl radicals, are preferably those with 1 to 12 carbon atoms, especially with 1 to 8 carbon atoms, insofar as they do not Say something else. These can be straight chain or branched chain and optionally can carry other substituents such as alkoxy with 1 to 4 carbon atoms, fluorine, chlorine, hydroxy, cyano, alkoxycarbonyl with 1 to 4 carbon atoms or COOH. Cycloalkyl radicals are preferably those having 3 to 7 carbon atoms, especially 5 to 6 carbon atoms. The alkenyl radicals are preferably those with 2 to 8 carbon atoms, especially with 2 to 4 carbon atoms. Aryl moieties, even those in the aralkyl moieties, are phenyl or naphthyl moieties, especially phenyl moieties. These may be substituted by 1 to 3 of the following radicals: alkyl having 1 to 6 carbon atoms, alkoxy with 1 to 6 carbon atoms, fluorine, chlorine, bromine, cyano, hydroxy, alkoxycarbonyl having 1 to 6 carbon atoms or nitro. Two contiguous residues can also form a ring. The term is heterocyclic, with 5 or 6-membered, aromatic or quasi-aromatic rings, optionally benzoalkylated, especially imidazole, benzimidazole, oxazole, benzoxazole, thiazole, benzothiazole, indole, pyrazole, triazole. thiophene, isothiazole, benzoisothiazole, 1,3,4- or 1,2,4-thiadiazole, pyridine, quinoline, pyrimidine and pyrazine. These can be substituted by 1 to 3 of the following radicals: alkyl with 1 to 6 carbon atoms, alkoxy with 1 to 6 atoms , carbon, fluorine, chlorine, bromine, cyano, nitro, hydroxy, mono or dialkylamino with 1 to 6 carbon atoms, alkoxycarbonyl with 1 to 6 carbon atoms, alkylsulfonyl with 1 to 6 carbon atoms, alkanoylamino with 1 to 6 carbon, phenyl or paphthyl atoms. Two contiguous residues can also form a ring. Electrochromic substances are known (Topics in Current Chemistry, Vol. 92, pages 1-44 (1980), Angew. Chem. 90, 927 (1978), Adv. Mater, 3, 225, (1991), DE-OS 3,917 .323, J. Am. Chem. Soc. Ul, 8528 (1995), JCS Perkin II 1990, 1777, DE-OS 4,435,211, EP-A 476,456, EP-A 476,457, DE-OS 4,007,058, J Org Chem. 57, 1849 (1992) and J. Am. Chem. Soc. 99, 6120, 6122 (1977) or can be obtained analogously The compounds of formula (L) are also known (WO 97 / 30134) The ions which are dependent on the synthesis, such as bromide, are finally exchanged for redox-inert ions. Particularly preferred in addition to the oxidizable compounds according to the invention of the formula (CC) or (COI) are the reducible electrochromic compounds of The formulas (I), (II), (III), (IV), (V) are very particularly preferred, in addition to the oxidizable compounds according to the invention, of the formula (CC) or (COI), the compounds reducible electrochromic formulas (I), ( IV), (V), where R :, R3, R8 and R9 mean, independently of each other. methyl, ethyl, propyl. butyl pentyl, hexyl, heptyl, benzyl, phenethyl, phenylpropyl, phenyl, 2-methylphenyl or 2,6-dimethylphenyl or Rs and R9 together form a bridge - (CH2) 2- or - (CH2) 3-, R10 to R13 mean hydrogen, R69 to R73, R80 and R81 mean, independently of each other, hydrogen or methyl R12, R69, R13, R70, R73, R80 and / or R74, R81 form a bridge -CH = CH-CH = CH-, Z1 means a direct bond or -CH = CH- and X "means an anion inepe low With redox conditions, the alkyl radicals, for example 2-butyl, 1-phenyl-2-propyl, can be branched. In the sense of the invention, the electrochromic compounds of the formula (I) are suitable in a very outstanding manner, where R.sup.2 and R3 are the same or different and mean methyl, ethyl, butyl, heptyl or phenylpropyl, R12 to R13 and R69 to R72 mean hydrogen, Z1 means a direct bond and X "means a redox-inert anion or means I". The electrochromic devices protected against light, according to the invention, contain in their electrochromic medium preferably at least one solvent, in which the electrochromic substances are dissolved, optionally a conductive salt and, if necessary, other additives. The solvent can also be expressed in the form of a gel, for example by polyelectrolytes, porous solids and nanoparticles with large active surfaces. Suitable solvents are all redox-inert solvents under the chosen stresses, which can not dissociate electrophiles or nucleophiles or which react as such in the form of electrophiles or of sufficiently powerful nucleophiles and, in this way, could react with the ions of the radicals colored. Examples in this regare propylene carbonate, α-butyrolactone, acetonitrile, propionitrile, benzonitrile, glutaronitrile, methylglutaronitrile, 3,3'-oxydipropionitrile, hydroxypropionitrile, dimethylformamide, N-methylpyrrolidone, sulfolane, 3-methylsulpholane or mixtures thereof. Preferred are propylene carbonate, benzonitrile and mixtures with one another or with glutaronitrile or 3-methylsulfolane. Particularly preferred is propylene carbonate. Also benzonitrile is particularly preferred. The electrochromic solution may contain at least one inert conductive salt. In particular, when at least one of the substances of the redox pair RED1 / OX2 is ionic in nature, the addition of a conductive salt can be abandoned. Suitable inert conducting salts are lithium, sodium and tetraalkylammonium salts, especially the latter. The alkyl groups may have between 1 and 18 carbon atoms and may be the same or different. Tetrabutylammonium is preferred. As anions for these salts, as well as anions X "in the formulas (I) to (VI), (O), (Oi) and (CV) to (CVII) and in the metal salts all the anions are considered colorless redox-ipertes.

Examples in this regard are tetrafluoroborate, tetraphenylborate, cyanothiphenylborate, tetramethoxybourate, tetrapropoxybrate, tetraphenoxybrate, perchlorate, chloride, nitrate, sulfate, phosphate, methanesulfopate, ethanesulfonate, tetradecanosulphonate, pentadecane sulphonate, trifluoromethanesulfonate, perfluorobutane sulfonate. perfluorooctanesulfonate, benzenesulfonate, chlorobenzenesulfopate, toluenesulphonate, butylbenzenesulfonate, tert-butylbenzenesulfonate, dodecylbenzenesulfonate, trifluoromethylbenzenesulfonate, hexafluorophosphate, hexafluoroacetate, hexafluorosilicate, 7,8,7,9-dicarbanide-undecaborate (-l) or (-2) which are optionally substituted at the B and / or F atoms with one or two methyl, ethyl, butyl or phenyl groups, dodecahydro-dicarbatedecaborate (-2) or B-methyl-C-phenyl-dodecahydro-dicarbatedeca-borate (-l) ). Also suitable as anions X "of the formulas (I) to (VI), (O), (Oi) and (CV) to (CVII) and in the metal salts, the aforementioned anions, which can also play the role of a REDi for example T, h 'The conductive salts are preferably used in the range from 0 to 1 mol / liter. As other additives, thickeners can be used to control the viscosity of the electroactive solution. This can be significant to avoid segregation, ie the formation of color formation in strips or spots in the case of prolonged operation of the electrochromic device in the connected state, and to control the speed of discoloration after the disconnection of the current . Suitable thickeners are all compounds customary for this purpose, such as, for example, polyacrylate, polymethacrylate (Luctite L®), polycarbonate or polyurethane. Other additives for the electrochromic solution are, for example, UV absorbers (<350 nm), the UV absorbers, for the desired protection, if appropriate. Examples in this regard are UVINUL® 3000 (2,4-dihydroxybenzophenone, BASF), SANDUVOR® 3035 (2-hydroxy-4-n-octyloxybenzophenone, Clariant), Tinuvin® 571 (2- (2H-benzotriazol-2-yl) -6-dodecyl-4-methylphenol, Ciba), Cyasorb 24 ™ (2,2'-dihydroxy-4-methoxy-benzophenone, American Cyanamid Company), UVINUL® 3035 (ethyl-2-cyano-3,3-diphenylacrylate, BASF), UVINUL® 3039 (2-ethylhexyl-2-cyano-3,3-diphenylacrylate, BASF), UVINUL® 3088 (2-ethylhexyl-p-methoxycinnamate, BASF), CHIMASSORB® 90 (2-hydroxy-4-methoxy) -benzophenone, Ciba). The last 4 mentioned are preferred. Mixtures of the UV absorbers, for example of the last four mentioned, are also preferred. The mixture formed by UVINUL® 3039 and CHIMASSORB® 90 is particularly preferred. The UV absorbers are used in the range of 0.01 to 2 mol / liter, preferably 0.04 to 1 mol / liter. The electrochromic solution contains the electrochromic substances OX2 t REDi, especially those of formulas (I) to (X) and (CC) and / or (COI), respectively in a concentration of at least 10"4 moles / liter, preferably from 0.001 to 0.5 moles / liter. The total concentration of all the electrochromic substances contained is preferably below 1 mol / 1. To operate the electrochromic device according to the invention, a constant, pulsating or variable-amplitude direct current, for example sinusoidal variable, is used. The voltage depends on the intensity of color desired, in particular, however, of the reduction or oxidation enhancers of the OX2 and REDi used, such potentials can be taken, for example, from the publications Topics in Current Chemistry, Volume 92, pages 1- 44, (1980) or Angew, Chem. 90, 927 (1978) or from the literature cited therein, the difference in their potentials is a value indicative of the necessary tension. to be made to work already with a lower tension or even with a higher tension. In many cases, for example when using OX2 = formula (I) or (V) and REDi = formula (CC) this potential difference, necessary for operation, is from <; 1 V. Such electrochromic devices can therefore be fed in a simple manner with the current coming from a silicon photovoltaic cell. If the voltage is disconnected, the electrochromic device according to the invention returns to its original state again. This dissipation can be considerably accelerated if the segments or the plates in contact are short-circuited. Signaling can also be distinguished in a very rapid manner by means of a multiple reversal of the voltage poles, possibly even with a simultaneous reduction of the voltage. By varying the layer thickness of the electrochromic device, the viscosity of the electrochromic solution and / or the ability to diffuse or move the electrochromic substances, the connection and disconnection times can be influenced within wide limits. of the signaling device. In this way, for example, the thin layers show shorter connection times than the thick layers. In this way, connectable devices can thus be constructed quickly and slowly and, thus, optimally adapted to the purposes corresponding to their use. In the case of slow devices, especially in signaling devices, a current or refreshment saving mode may be employed for the maintenance of the displayed information in the connected state. After the establishment of the information to be displayed, for example by means of constant direct current or that varies with high frequency or pulsating, of sufficient amplitude is switched to the pulsating constant or variable low frequency voltage, the contacts of the segments are not short circuited. during the phases in which the voltage is zero. This low frequency can be found, for example, in the range of 1 Hz or less than this value, the length of the connection and disconnection phases not being equal, but, for example, the connection phases can be clearly longer. Since, during the pauses of the current in the non-short-circuited state, the color intensity of the displayed information decomposes only slowly, relatively short current pulses are sufficient to compensate for these losses again in the subsequent refresh phase. In this way, an image free of spots with an almost constant color intensity is obtained, for which maintenance only a fraction of the current that would be required with a permanent flow of the current is required. Special forms of embodiment of the aforementioned types 1 and 2 can be, for example, the following, which also constitute an object of the invention, when they contain electrochromic substances according to the invention. Type 1: (not speculate). In the area of light protection / light filter: windows for building windows, road vehicles, airplanes, trains, boats, glazed roofs, self-cleaning roofs, glazing of greenhouses and winter gardens, light filters any kind; in the field of security / confidentiality: separating plates for the division of office space, motor vehicles for roadways, airplanes, trains, protective plates against vision in the counters of banks, glazed doors, plates for motorcycle helmets and for pilots; in the design sector: glazing of ovens, microwave appliances, other household appliances, furniture. In the field of representation: analog voltage signaling devices, such as battery testers, tank indicators, temperature indicators. Type 1: (speculate). Mirrors of any kind for motor vehicles for roadways, trains, especially flat, spherical, aspherical mirrors and combinations thereof such as spherical / aspherical specular glazing in furniture. Type 2: Signaling devices of any type, segment or matrix markers for watches, computers, electrical appliances, electronic devices, such as radios, amplifiers, televisions, CD vectors, destination indicators on buses and trains, departure and arrival indicators of aircraft at stations and airports , flat screens, all applications that have been cited in the case of type 1 and 2, containing at least one switchable, static or variable signaling device such as separation plates, which contain indications such as "please do not disturb", "window out of service", mirrors for automobiles, containing indications of any kind such as the indication of temperature, failures in the motor vehicle, for example oil temperature, open doors, time, astronomical direction. Another object of the invention are the hydrophenazines of the formula (CC). wherein R201 means aryl, especially aryl with 6 to 10 carbon atoms, R202 means alkyl with 2 to 12 carbon atoms, cycloalkyl with 3 to 7 carbon atoms, alkenyl with 2 to 12 carbon atoms or aralkyl with 7 to 16 carbon atoms, R203 and R204 mean, independently of each other, hydrogen, halogen, alkyl having 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, cyano or aryl with 6 to 10 carbon atoms, myn mean, independently of each other, an integer from 1 to 4 or two contiguous R203 and R204 mean, independently of each other, a bivalent moiety -CH = CH-CH = CH-, as long as n means >; 2. Especially in the dihydrophenazines of the formula (CC) R201 means phenyl, which may optionally carry up to 3 methyl, methoxy, chloro, bromo or cyano radicals, R202 means alkyl having from 2 to 8 carbon atoms, if appropriate branched, cyclopentyl, cyclohexyl, benzyl, phenethyl or phenylpropyl, R203 and R204 mean, independently of one another, hydrogen, chlorine, bromine, methyl, ethyl, propyl, butyl, methoxy, ethoxy, cyano or phenyl. m and n signify, independently of each other, an integer from 1 to 2 or two contiguous R203 and R204 signify, independently of each other, a bivalent moiety -CH = CH-CH = CH-, when m or n means 2.

Very particularly preferably in the dihydrophenazines of the formula (CC). R201 means phenyl, R202 means ethyl, propyl, butyl, phenylethyl or phenylpropyl. R203 and R204 mean hydrogen and m and n mean 1. Another object of the invention are the dihydrophenazines of the formula (COI), in which R202 means alkyl, cycloalkyl, alkenyl, aralkyl or aryl, especially means alkyl with 1 to 12 carbon atoms, cycloalkyl with 3 to 7 carbon atoms, alkenyl with 2 to 12 carbon atoms, aralkyl with 7 to 16 carbon atoms or aryl with 6 to 10 carbon atoms, B means a bivalent bridge, especially means - (CH2) P- , -CH2- (O-CH2) qO-CH2- or - (CH2) -C6H4- (CH2) s-, where the group CH2- can be substituted by methyl, R203 and R204 mean, independently of each other, hydrogen, halogen , alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, cyano or aryl with 6 to 10 carbon atoms, and n mean, independently of each other, an integer from 1 to 4 or two contiguous R203 and R204 , independently of each other, they mean a bivalve rest entity -CH = CH-CH = CH-, when m or n mean > 2, p means an integer from 2 to 20 and q, r and s mean, independently of each other, an integer from 0 to 10. Especially in the dihydrophenazines of the formula (COI), R20; means alkyl having from 2 to 8 carbon atoms, if appropriate branched, cyclopentyl, cyclohexyl, benzyl, phenethyl, phenylpropyl, or phenyl, where said radicals may carry up to three methyl, methoxy, chloro, bromo or cyano radicals, B means - (CH? V, R203 and R204 stand for, independently of one another, hydrogen, chlorine, bromine, methyl ethyl, propyl, butyl, methoxy, ethoxy, cyano or phenyl, and mn mean, independently of each other, an integer from 1 to 2 or two. R203 and R204 contiguous means, independently of each other, a bivalent moiety -CH = CH-CH = CH-, when either n means 2, and p means an integer from 2 to 10. Very particularly preferably in the dihydrophenazines of the formula (COI), R202 means methyl, ethyl, propyl, butyl, phenethyl, phenylpropyl or phenyl, B means - (CH? V, R203 and R2 <M sigpiflcan hydrogen, m and n mean 1, p means an integer of 3 to 5. In a very special way in the dihid rofenazines of the formula (COI), R202 means phenyl, B means - (CH2) P-, R203 and R204 mean hydrogen, m and n mean 1, p means 3 or 4.

E jen, pious. Example 1. A cell according to figure 1 was constructed. For this, two glass plates 1 and 2 were used, which are coated on a surface with ITO. A mixture consisting of 97 9c of DELO-Katiobond® 4594 light-curing epoxy adhesive (DELO Industrieklebstoffe, Landsberg) and 3% of glass balls with a diameter of 200 μm, in the form of a ring (3, see Figure 1) was applied. on the ITO-coated side of the glass plates 1, in such a way that a hole with a width of 2 mm was formed (4, see Figure 1). Next, the glass plate 2 was placed on the glue worm in such a way that the ITO layers of both plates 1 and 2 were directed to each other and a geometry was formed as shown in figure 1. The hardening of the glue it was carried out by lighting for 10 minutes with daylight in the vicinity of a window and then without illumination for 20 minutes at 105 ° C. A capsule was filled, under a nitrogen atmosphere, with a solution that was 0.02 molar in the electrochromic compounds of the formulas 2 BF. respectively 0.1 molar in the UV absorbers of the formulas (CCCXI) in anhydrous propylene carbonate, free of oxygen. The cell was then placed, under a nitrogen atmosphere, perpendicularly in the capsule in such a way that the orifice 4 was below the level of the liquid. The capsule with the cell was placed in a desiccator. This was subjected to a vacuum of 0, 05 mbar and then carefully vented with nitrogen. During the ventilation the electrochromic solution rose through hole 4 to the cell and filled, with the exception of a small bubble, the entire volume. The cell was removed from the solution, cleaned under a nitrogen atmosphere in hole 4, by means of wiping with a paper towel, and closed with a photochemically hardenable acrylate adhesive DELO-Photobond® 4497 (DÉLO Industrieklebstoffe, Landsberg) . It was then illuminated for 1 minute under a nitrogen atmosphere with the DELOLUX® 03 lamp (DÉLO Industrieklebstoffe, Landsberg) which was at a distance of 8 cm from the hole 4 and hardened at room temperature overnight under a nitrogen atmosphere. By applying a voltage of 0.9 V on the two plates 1 and 2, the cell quickly colored dark greenish blue. By disconnecting the voltage and short-circuiting the contacts, the coloration quickly disappeared again. In a completely analogous manner, the electrochromic compounds of the following examples 2 to 12 were used: It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Claims (12)

1. Having described the foregoing invention, the claim contained in the following claims is claimed as property: 1. Electrochromic device, which contains a pair of glass or plastic plates or sheets of synthetic material, between whose plates or sheets at least one , preferably both plates or sheets are respectively provided on one side with an electrically conductive coating, between whose plates or sheets at least one, and its conductive coating, are transparent, the other being able to be mirror-like and between which at least one of the two plates or sheets the electrically conductive layer can be subdivided into separate, individually contacted surface segments, the plates or sheets being joined by means of a sealing ring on the side of its conductive coating, and the volume, formed by the two plates or sheets and by the joint ring is filled with an electrochromic medium, which contains a p of electrochromic substances OX2 and REDi, characterized in that REDi corresponds to one of the formulas
2. (CCIII) where R201 means aryl, R202 means alkyl, cycloalkyl, alkenyl, aralkyl or aryl, B means a bivalent bridge, R203 to R206 independently of one another, meaning hydrogen, halogen, alkyl, alkoxy, cyano or aryl, m and n independently of each other means a number integer from 1 to 4 or two contiguous R203 and R204, independently of each other, means a bivalent moiety -CH = CH-CH = CH-, when either n means > 2. Electrochromic device according to claim 1, characterized in that REDi corresponds to one of the formulas (CC), (CO), (COI) or (COII), where R201 means aryl with 6 to 10 carbon atoms, R202 means alkyl with 1 to 12 carbon atoms, cycloalkyl with 3 to 7 carbon atoms, alkenyl with 2 to 12 carbon atoms, aralkyl with 7 to 16 carbon atoms or aryl with 6 to 10 carbon atoms,
3. B means - (CH-), - (CHzMO-CH- q-OCH.- or - (CH2) r-C6H4- (CH2) s-, where the
4. CH2- group can be substituted by methyl,
5. R203 to R206 independently of one another, they mean hydrogen, halogen, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms carbon, cyano or aryl with 6 to 10 carbon atoms, m and n independently of each other, means an integer from 1 to 4 or two contiguous R203 and R204, independently of each other, mean a bivalent radical -CH = CH-CH = CH- , when well n means > 2, p means an integer from 2 to 20 and q, r and s independently from each other, mean an integer from 0 to 10. 3. Electrochromic device according to claim 1, characterized in that REDi corresponds to one of the formulas (CC), (CO), (COI) or (CCIII), where R201 means phenyl, which can optionally carry up to three methyl, methoxy, chloro, bromo or cyano residues, R202 means alkyl with 1 to 8 carbon atoms, if appropriate branched , cyclopentyl, cyclohexyl, benzyl, phenethyl, phenylpropyl or phenyl, these residues may, if appropriate, carry up to three methyl, methoxy, chlorine, bromine or cyano residues, B means - (CH2) P-, R203 to R206 independently of each other, meaning hydrogen, chlorine, bromine, methyl, ethyl, propyl, butyl, methoxy, ethoxy. cyano or phenyl, m and n independently of each other, mean an integer from 1 to 2. or two contiguous R203 and R204, independently of each other, mean a bivalent moiety -CH = CH-CH = CH-, when n or n means 2 and p means an integer from 2 to 10. 4. Electrochromic device according to claim 1, characterized in that REDi corresponds to the formula (CC), wherein R201 means phenyl, R202 means methyl, ethyl, propyl, butyl, fepylpropyl or phenyl , especially preferably phenyl, R203 and 204 sjgnjflca hydrogen and m and n mean 1. 5. Electrochromic device according to claim 4, characterized in that R2o. and R20 Signifjcan phenyl.
6. 6. Electrochromic device according to claim 1, characterized in that REDi corresponds to the formula (COI), where R202 means phenyl, B means - (OhV, R203 and R2w mean hydrogen, m and n mean 1 and p means an integer from 2 to 6.
7. 7. - Electrochromic device according to claim 6, characterized in that R202 means phenyl and p means 4.
8. 8. Electrochromic device according to claim 1, characterized in that it contains as OX2 a compound selected from the formulas 4X- '¿^ (III), 2X- 2X- 2X- ,twenty R, 0 \, 103 N-N ' where R2 to R5, R8, R9, R16 to R19 means alkyl with 1 to 18 carbon atoms, alkenyl with 2 to 12 carbon atoms, cycloalkyl with 4 to 7 carbon atoms, aralkyl with 7 to 15 carbon atoms or aryl with 6 to 10 carbon atoms or R 4; R5 or R8; R9 can together form a bridge - (CH2) 2- or - (CH2) 3-, R6, R7 and R22 to R25, independently of each other, mean hydrogen, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 atoms carbon, halogen, cyano, nitro or alkoxycarbonyl having 1 to 4 carbon atoms or R22, R23 and / or R24; R25 can form a bridge -CH = CH-CH = CH-, R10; R ", R10, R13, R12, R13 and R14, R15 independently of each other, means hydrogen or in a paired form means a bridge - (0.2) 2-, - (CH2) 3- or -CH = CH-, R20 and R21 independently of one another, they mean O, N-CN, C (CN) 2 or N-aryl with 6 to 10 carbon atoms, R26 and R27 mean hydrogen, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, carbon, halogen, cyano, nitro, alkoxycarbonyl with 1 to 4 carbon atoms or aryl with 6 to 10 carbon atoms R69 to R74, R80 and R81 independently of one another, mean hydrogen or alkyl having 1 to 6 carbon atoms or R69, R12, R70, R13, R73, R80 and / or R74, R81 together form a bridge -CH = CH-CH = CH-, E1 and E2 independently of each other, mean O, S, NR1 or C (CH3)? or E1 and E2 together form a bridge -N- (CH2) 2-N, R1 means alkyl with 1 to 18 carbon atoms, alkenyl with 2 to 1 carbon atoms, cycloalkyl with 4 to 7 carbon atoms, aralkyl with 7 up to 15 carbon atoms, aryl with 6 to 10 carbon atoms. Z1 means a direct bond, -CH = CH-, -C (CH3) = CH-, -C (CN) = CH-. -CC1 = CC1-, -C (OH) = CH-, -CC1 = CH-, -C = C-, -CH = NN = CH-, C (CH3) = NN = C (CH3> - or - CC1 = NN = CC1-, Z2 means - (CH2) r- or -CH2-C6H -, - CH2-, r means an integer from 12 to 10, R94 and R95 independently of each other, mean hydrogen or cyano, R101 up to R105, independently of one another, mean aryl with 6 to 10 carbon atoms or a heterocyclic ring with 5 or 6 members, aromatic or almost aromatic, optionally benzo-ring, R107, R109, R113 and R114 independently of one another, mean a residue of the formulas (CV) up to (CVII) RIOE Ru5 and R? i6 independently of each other. they mean aryl with 6 to 10 carbon atoms or a residue of the formula (CV). Rpo up to R112, R117 and R "8 independently of one another, mean hydrogen, alkyl having 1 to 4 carbon atoms, halogen or cyano, E101 and E'02 independently of each other mean O, S or NR" 9, R? I9 and R? _2 independently from one another, mean alkyl with 1 to 18 carbon atoms, alkenyl with 2 to 8 carbon atoms, cycloalkyl with 4 to 7 carbon atoms, aralkyl with 7 to 15 carbon atoms or aryl with 6 to 10 atoms of carbon, R106, R120, R121, R123 and R124 independently of each other, mean hydrogen, alkyl having 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, halogen, cyano, nitro or alkoxycarbonyl having 1 to 4 carbon atoms. carbon or R120, R'21 or R123, R124 together form a bridge -CH = CH-CH = CH-, A1, A2 and A3 independently of each other mean O or C (CN) ?, R96 means hydrogen, phenyl or tere . -butyl and X "means an inert anion under the redox conditions
9. 9. -Employment of the electrochromic device according to claim 1 as a window or as a separation plate or as a plate for protection against sight or glass or glazing for roofs or filter light or as a mirror or as a signaling device
10. 10. -Dihydrofenazines of the formula (CC), wherein R201 means aryl with 6 to 10 carbon atoms R202 means alkyl with 2 to 12 carbon atoms, cycloalkyl with 3 to 7 carbon atoms, alkenyl with 2 to 12 carbon atoms or aralkyl with 7 to 16 carbon atoms , R203 and R204 mean, independently of one another, hydrogen, halogen, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, cyano or aryl with 6 to 10 carbon atoms, myn mean, independently of each other, an integer from 1 to 4 or two contiguous R203 and R204, independently of one another, means a bivalent moiety -CH = CH-CH = CH-, when n or n mean > 2.
11. 11.- Dihydrofenazines of the formula (COI), wherein R20: means alkyl with 1 to 12 carbon atoms, cycloalkyl with 3 to 7 carbon atoms, alkenyl with 2 to 12 carbon atoms, aralkyl with 7 to 17 carbon atoms or aryl with 6 to 10 carbon atoms . B means - (CH? V, -CH2, - (O-CH2) qO-CH2- or - (CH? C? H? -CH? V, CH2- groups being substituted by methyl, R203 and R204 mean, independently of each other , hydrogen, halogen, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, cyano or aryl with 6 to 10 carbon atoms, m and n mean, independently of each other, an integer from 1 to 4 or two R203 and R204 contiguous means, independently of each other, a bivalent moiety -CH = CH-CH = CH-, when either n signifies > 2, p means an integer from 2 to 20 and q, r and s, independently of each other, an integer from 0 to 10.
12. 12.- Electrochromic medium, containing a pair of electrochromic substances OX2 and REDi, characterized in that REDi corresponds to one of the formulas (CCIII) wherein R201 means aryl, R202 means alkyl, cycloalkyl, alkenyl, aralkyl or aryl, B means a bivalent bridge, R203 to R206 mean, independently of one another, hydrogen, halogen, alkyl, alkoxy, cyano or aryl, and m mean independently of each other , an integer from 1 to 4 or two contiguous R203 and R204 mean, independently of each other, a bivalent moiety -CH = CH-CH = CH-, when n or n mean > 2. . IMPROVED. SUMMARY OF THE INVENTION The use of certain dihydronaphthazines or dihydrophenazines in electrochromic devices leads to improved stability in the light of electrochromic devices.