JP3538019B2 - Photochromic crystal material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel compound useful as a photochromic material, which reversibly generates two isomers having different colors by the action of light, and converts light information into chemical information called structural change of a molecule. TECHNICAL FIELD The present invention relates to a photochromic material including a photochromic molecule or a molecular assembly having a function to perform, and an optical functional electronic device containing the same.

[0002]

2. Description of the Related Art A photochromic material is a material containing molecules or molecular aggregates that reversibly generate two isomers having different colors by the action of light. This photochromic material reversibly changes not only color but also various physical properties such as refractive index, dielectric constant, and oxidation / reduction potential by light irradiation, and is expected to be applied as an optical functional material, particularly as an optical memory or optical switch. Have been. Conventional photochromic molecules or molecular aggregates can only function when dissolved in a medium (molecule-dispersed state). Therefore, when used in a solid state, they need to be dispersed in a polymer film or the like. there were. However, when dispersed in a polymer film, the rigidity of the medium reduces photochromic reactivity, resulting in poor durability and repeated use problems. And it is difficult to increase the sensitivity.

On the other hand, recently, a thermally stable photochromic molecule or molecular assembly such as a maleic anhydride derivative has been reported (JP-A-5-39289), but the photochromic reactivity in a crystalline state was not sufficient. The present inventors have also reported that a molecule satisfying photochromic reactivity in a crystalline state is a diaryl perfluorocyclopentene derivative (Irie et al., Molecular Crystal Liquid Crystal, Vol. 81, p. 297). (1997) (M.Ir
ie, et al., Mol. Cryst. Liq. Cryst, 81, 297, 199
7)), The crystals of the diaryl perfluorocyclopentene derivative are colored by irradiation with ultraviolet light, and return to the original state by irradiation with visible light. This coloring state is stable and 1
It is reported that it does not fade even at 00 ° C. However, when this crystal is to be used as a photochromic material in a single crystal state, the crystal has physical fragility and has a problem in practicality.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of such circumstances, and an object of the present invention is to exhibit photochromic reactivity in a crystalline state without using a polymer medium, An object of the present invention is to provide a hard photochromic crystal material that has physical strength enough to withstand repeated use and is thermally stable.

The present inventor has conducted further studies to solve the above-mentioned drawbacks. In order to eliminate the physical fragility of the crystal of the diaryl perfluorocyclopentene derivative while maintaining the photochromic reactivity, the present inventors have proposed a method in which a molecule is located at a long distance. It has been found that it is sufficient to introduce at least one ionic bond having an acting Coulomb force into the heteroaryl moiety of the diheteroarylethene-based compound, and the present invention has been completed.

[0006]

That is, the present invention provides the following general formula (I):

[0007]

Embedded image (Wherein A and B may be the same or different from each other, and each independently represents the following general formula (II):

[0008]

Embedded image (Wherein Y is an oxygen atom, a sulfur atom, a selenium atom or N
Represents -R ^4, W represents a nitrogen atom or C-R ^5,
R ¹ , R ² , R ³ and R ⁵ are the same or different and are each independently a bond to a perfluoropentene ring, a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, Or an unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkenyl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkoxyl group,
Represents a halogen atom, a trifluoromethyl group, a cyano group, or a substituted or unsubstituted aryl group, or
^Two adjacent R ¹ , R ² , R ³ , and R ⁵ may be bonded together to have a substituent, and at least one carbon atom in the chain is a hetero atom. Represents a saturated or unsaturated alkylene group or alkenylene group, which may be substituted, and R ⁴ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, or a substituted or unsubstituted group; Represents an aryl group. Where R
^{At least one} of R ¹ , R ² , R ³ and R ⁵ is a bond to a perfluoropentene ring, and a heterocyclic group of the general formula (II) is bonded to a perfluoropentene ring of the general formula (I). And ^{three of} the remaining R ¹ , R ² , R ³ , and R ⁵ are not simultaneously hydrogen atoms, and the remaining R ¹ , R ² ,
At least one of the three groups of R ³ and R ⁵ is an aryl group substituted with an ionic substituent. ) Represents a heterocyclic group. The present invention relates to a diheteroarylethene compound having at least one ionic substituent in a heterocyclic group represented by the formula (1) and a solvate thereof. As the ionic substituent of the substituted aryl group, a carboxyl group, a sulfonic acid group, a pyridinium group or an ammonium group is preferable, and as a counter ion of these ionic substituents, an alkali metal cation, an alkaline earth metal cation, Organic base cations, halogen anions, PF ₆ ⁻ or organic acid anions are preferred.

More specifically, the present invention relates to a compound represented by the general formula (II) wherein the groups represented by the general formula (II) of the groups A and B in the general formula (I) are mutually sterically hindered. The diheteroarylethene compound according to any one of claims 1 to 3, and a solvate thereof. More specifically, the present invention provides compounds of the general formula (I
The group represented by I) is a 2-ionic group-substituted aryl-5
The present invention relates to a diheteroarylethene compound which is a -substituted-thiophen-4-yl group or a 2-ionic group-substituted aryl-5-substituted-thiazol-4-yl group, and a solvate thereof.

[0010] The present invention also relates to a photochromic crystal material comprising a diheteroarylethene compound represented by the general formula (I) or a solvate thereof. Further, the present invention provides an optical functional electronic device, preferably an optical memory or an optical switch display, comprising a photochromic crystal material comprising a diheteroarylethene compound represented by the general formula (I) or a solvate thereof. About.

The present invention provides a diheteroarylethene compound molecule or molecular crystal having a structure in which a compound of the general formula (I) and a counter ion of an ionic substituent thereof are bonded to each other. To provide a robust photochromic material that reversibly generates two isomers having different colors. Photochromic materials are used not only for light modulating materials, but also for optical devices, so they must have performance such as repetition durability, high sensitivity, and semiconductor laser sensitivity in addition to thermal stability. The material satisfies the requirements, and particularly when used in an optical memory or an optical switch, has a remarkably high repetition durability due to a large increase in hardness of the material.

The compound represented by formula (I) of the present invention will be described in more detail. The present inventors have previously reported the compound represented by the general formula (I) as a photochromic crystal material (Irie et al., Molecular Crystal Liquid Crystal, Vol. 81, p. 297 (1997).
(M.Irie, et al., Mol. Cryst. Liq. Cryst, 81, 2
97, 1997)) is a kind of diaryl perfluorocyclopentene derivative having a perfluorocyclopentene ring as a basic structure. However, the general formula (I) of the present invention
Are markedly different in that they have an ionic substituent such as a carboxyl group, a sulfone group, or a quaternary ammonium group in the molecule. That is, by introducing such an ionic substituent into the molecule,
As a result, a crystalline compound having extremely excellent physical strength as a crystal was obtained while maintaining the properties as a photochromic material. Therefore, the compound represented by the general formula (I) of the present invention is characterized in that it has an ionic substituent in the molecule, and in other respects, it has properties as a photochromic material. And all conventional compounds having the formula:

Further, the compound represented by formula (I) of the present invention will be described in more detail. The compound represented by the general formula (I) of the present invention has a heterocyclic group having an aromatic attribute at the 1-position and the 2-position of the perfluoropentene ring. More specifically, these heterocyclic groups are represented by the general formula (II).

In the general formula (II), Y represents an oxygen atom, a sulfur atom, a selenium atom or N—R ⁴ , and W represents a nitrogen atom or C—R ⁵ to form a 5-membered heterocyclic ring. are doing.
Preferred heterocycles include thiophene, thiazole, pyrrole, imidazole, furan, oxazole and the like. A thiophene ring and a thiazole ring in which X is a sulfur atom are more preferred heterocycles.

The alkyl group in R ¹ , R ² , R ³ , and R ⁵ in the general formula (II) is a chain having 1 to 30, preferably 1 to 20, more preferably 1 to 10 carbon atoms. A branched alkyl group is preferable, and a lower alkyl group or an alkenyl group is more preferably a chain or branched alkenyl group having 2 to 30, preferably 2 to 20, and more preferably 2 to 10 carbon atoms. Preferably, more preferably, the lower alkenyl group and the cycloalkyl group have 5 to 3 carbon atoms.
0, preferably 5 to 20, more preferably 6 to 10 monocyclic, polycyclic or fused cyclic alkyl groups are preferred,
The cycloalkenyl group is preferably the above-mentioned cycloalkyl group having at least one unsaturated bond, and the aryl group is preferably a carbon group having 6 to 30, preferably 6 to 20, more preferably 6 to 10 carbon atoms. Is preferably a monocyclic, polycyclic or condensed cyclic aryl group, and the heterocyclic group has at least one nitrogen atom, oxygen atom or sulfur atom in the ring, and has one ring size. Is 5-20
Member, preferably 5 to 10 members, more preferably 5 to 7 members, and a saturated or unsaturated monocyclic, polycyclic or fused ring which may be condensed with the cycloalkyl group, cycloalkenyl group or aryl group described above. The heterocyclic group of the formula is preferable, and examples of the aralkyl group include those in which the above-mentioned alkyl group or alkenyl group is substituted with the above-mentioned aryl group or heterocyclic group. Examples of the alkoxy group include the above-mentioned alkoxy group having an alkyl group.

In the general formula (II), the above-mentioned alkyl group, alkenyl group, cycloalkyl group, cycloalkenyl group,
The aryl group, the heterocyclic group, the aralkyl group or the alkoxy group may be further substituted with a substituent as long as the properties as the photochromic material of the present invention can be maintained. In the general formula (II), as the substituent of the above-mentioned alkyl group, alkenyl group, cycloalkyl group, cycloalkenyl group, aryl group, heterocyclic group, aralkyl group or alkoxy group, these groups are mutually substituted. Where possible, these groups may be substituted for each other. Examples include an alkyl-substituted cycloalkyl group, an alkyl-substituted aryl group, an alkyl-substituted heterocyclic group, an alkyl-substituted aralkyl group, a cycloalkylalkyl group, a cycloalkylalkenyl group, and an alkenyl-substituted aryl group.

Other substituents include an alkoxy group comprising the above-mentioned alkyl group, an alkylthio group, a dialkylamino group, a halogen atom such as chlorine, bromine and fluorine;
Examples thereof include an alkylenedioxy group such as a methylenedioxy group and a 2,2-dimethylmethylenedioxy group, and a cyano group. Preferred substituents include a methyl group, an ethyl group,
Lower alkyl groups such as n-propyl group, isopropyl group and t-butyl group, aryl groups such as phenyl group and naphthyl group, lower alkoxy groups such as methoxy group, ethoxy group and n-propoxy group, dimethylamino group and diethylamino group And di-lower alkylamino groups such as dipropylamino group, halogen atoms such as chlorine and fluorine, alkylenedioxy groups such as methylenedioxy and 2,2-dimethylmethylenedioxy group, and cyano group.

Further, R ¹ , R ² , R 3 of the general formula (II)
³ , R ⁵ include halogen such as chlorine atom, fluorine atom and bromine atom, trifluoromethyl group, cyano group and the like. R ¹ , R ² , R ³ , and R ⁵ in the general formula (II) are
^Two adjacent R ¹ , R ² , R ³ , and R ⁵ may be bonded together to have a substituent, and at least one carbon atom in the chain is a hetero atom. It may be a saturated or unsaturated alkylene group or alkenylene group which may be substituted.

Specific examples of R ¹ , R ² , R ³ and R ^{5 in} the general formula (II) include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl and t-butyl. Lower alkyl groups such as butyl group and hexyl group; lower alkenyl groups such as vinyl group, propenyl group and butenyl group; cycloalkyl groups such as cyclohexyl group and cyclopentyl group; cycloalkenyl groups such as cyclohexenyl group; phenyl group and naphthyl group Aryl group such as, thienyl group,
Examples include a heterocyclic group such as a furanyl group, an aralkyl group such as a benzyl group and a phenethyl group, a lower alkoxy group such as a methoxy group, an ethoxy group, and an n-propoxy group, a trifluoromethyl group, and a cyano group. Further, these groups may have the above-mentioned substituents.

The alkyl group, cycloalkyl group or aryl group of R ^{4 in} the general formula (II) includes the above-mentioned alkyl group, cycloalkyl group and aryl group.

In the present invention, R ¹ , R ² , R
^At least one of R ³ and R ⁵ is a bond to the perfluorocyclopentene ring, and this bond connects the heterocyclic group of the general formula (II) to the perfluoropentene ring of the general formula (I). . The position at which the heterocyclic group of the general formula (II) is bonded to the perfluorocyclopentene ring may be any of the 2-, 3-, and 4-positions of the heterocyclic group.

In the present invention, R ¹ , R ² , R 3 of the general formula (II)
^At least one of R ³ and R ⁵ is a bond to a perfluorocyclopentene ring, and the remaining R ¹ , R ² , R ³ and R ⁵
Three of the groups may be the above-mentioned groups or hydrogen atoms, but these three groups cannot be hydrogen atoms at the same time. At least one of these remaining three groups is a group other than a hydrogen atom. In order to explain this more concretely, the reversible reaction of the compound of the present invention by light is shown by the following reaction formula based on one specific compound of the present invention. Show.

[0023]

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Wherein X is the same as Y in the general formula (II), and Z is the same as R ^1. The compound (III) of this reaction formula is cyclized by receiving light to give the compound (IV) )become. Then, the compound (IV) emits light and reversibly returns to the compound (III). At this time, mutual cyclization occurs at a position adjacent to a position where the heterocyclic group of the substituents A and B of the general formula (I) is bonded to the perfluorocyclopentene ring. When the group bonded to the position of the heterocyclic ring of the substituents A and B that forms a new 6-membered ring is a hydrogen atom by this cyclization reaction, the hydrogen atom is eliminated by the cyclization reaction. It is preferable that a group other than a hydrogen atom be substituted at this position of the two heterocyclic groups. That is, a preferred embodiment of the compound represented by the general formula (I) of the present invention is represented by the general formula (II) of the A and B groups in the general formula (I). Compounds which are adjacent to the position of the group bonded to the perfluoropentene ring and in which the compound of the general formula (I) undergoes light cyclization at a position other than a hydrogen atom can be mentioned.

At least one of the remaining three groups among R ¹ , R ² , R ³ and R ⁵ is an aryl group substituted with an ionic substituent. As the ionic group of the present invention, any one can be used as long as a cation and an anion can form a single functional group as a pair. Examples of the anionic group include a carboxylate anion and Sulfonate anions, phosphate anions and the like can be mentioned, and those forming a cationic group include, for example, a pyridinium cation and a quaternary ammonium cation. Examples of counter ions of these ions include metal ions, particularly alkali metal ions, alkaline earth metal ions, and halogen ions (chlorine ions, bromine ions, and the like), in addition to the above-described ions. Examples of the alkali metal ion include sodium, potassium and cesium ions. Examples of the alkaline earth metal ion include calcium and magnesium ions. Examples of the organic base cation include an aliphatic quaternary ammonium ion and an aromatic quaternary ammonium ion.
Examples of the organic acid anion include anions derived from aliphatic saturated carboxylic acids, unsaturated lower carboxylic acids, p-toluenesulfonic acid, and the like.

The group A of the present invention represented by the general formula (II)
Or, if preferred examples of B are shown, the following general formula (V):
(VI), (VII) and (VIII).

[0027]

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[0028]

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[0029]

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[0030]

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Wherein Y, R ¹ , R ² , R ³ , R ⁴ and R ⁵
Is the same as described above, Z is the same as Y described above, and the single line represents a single bond bonded to the perfluorocyclopentene ring. Each of these aromatic heterocyclic groups can be independently bonded to the position A or B of the perfluorocyclopentene ring. The group represented by the general formula (V) is represented by the general formula (II)
Is an example in which R ² is a bond and W is C—R ⁵ , and the group represented by the general formula (VI) is a group represented by the general formula (I
Examples of the compound represented by I) wherein Y is Z, R ¹ is a bond, and W is C—R ⁵ , and the group represented by the general formula (VII) is a group represented by the general formula (II) wherein R ² is In the group represented by the general formula (VIII), Y is Z, R ¹ is a bond and W is a nitrogen atom in the general formula (II). Are illustrated. As more specific examples of these groups, those in which Y is a sulfur atom are particularly preferable.

A more specific example of the compound represented by the general formula (I) in which the group represented by the general formula (II) is bonded to a perfluorocyclopentene ring is given by the following general formulas (IX) and (IX). X), (XI) and (XII).

[0033]

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[0034]

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[0035]

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[0036]

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(Wherein R ¹ , R ² , R ³ , R ^4, R ⁵ , and
R ⁷ is the same as R ¹ , R ² , R ³ and R ^{5 in} the general formula (II). The compound of the general formula (I) of the present invention is a compound not described in the literature. By controlling the mixing ratio of perfluorocyclopentene and aryl halide, monoarylcyclopentene containing only one aryl group can be selectively used. It can be synthesized, and as described above, symmetric and asymmetric diarylethene can be easily synthesized. The general formula (I) compound crucible production method of the present invention represented by the general formula (V) (where X in the formula represents a Y in the general formula (V).) R ¹ is a methyl group in The following is an example of a reaction formula taking the above case as an example.

[0038]

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[0039] (wherein, Z is a group of the lithiated such as a halogen, R ³ represents a R ² of the general formula (II), R ²
Represents R ³ of the general formula (II), and R ⁶ and R ⁷ are each independently the same or different and are each R ² or R ³ of the general formula (II)
Is shown. )

An example of a method for introducing an aryl group as a substituent of the aromatic heterocyclic group represented by the general formula (II) is shown in the following reaction formula. The metallizable position of the aromatic heterocyclic compound can be metallized with an alkali metal or an alkaline earth metal, and an aryl group can be introduced by reacting the metal with an aryl halide such as phenyl iodide.

[0041]

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In this example, an unsubstituted phenyl group is exemplified as the aryl group. However, if necessary, various inert substituents, ionic groups, or groups which are precursors thereof may be substituted. Is also good.

[0043]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The present invention has found that a diheteroarylethene salt compound having at least one ionic substituent on a heteroaryl exhibits photochromic reactivity in a hard crystalline state. Specific examples of such compounds include the following compounds.

[0044]

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A carboxyphenyl group is added to the 5 of the thiophene ring.
Then, an ionic crystal containing an alkali metal ion was prepared by reaction with the alkali metal ion. Na, K, and Cs ions were used as the alkali metal ions. The maximum absorption values of the ring-closed forms of this compound are shown in Table 1 below.

[0046]

[Table 1]

Each crystal was colored blue when irradiated with ultraviolet light, and the blue color was faded when irradiated with visible light. FIG. 1 shows an absorption spectrum when the cation described above is a sodium ion.

[0048]

EXAMPLES Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples unless it exceeds the gist thereof.

Embodiment 1

[0050]

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A diarylethene having a sodium ion was prepared in the following manner. Methanol 10 ml, 5
0 mg of 1,2-bis (2-methyl-5- (4-carboxyphenyl) -thiophen-3-yl) perfluorocyclopentene (1,2-bis (2-methyl-5- (4-carboxyphene)
Dissolve yl) -thiophen-3-y1) perfluorocyclopentene). An aqueous solution containing 2 equivalents of Na0H is added thereto, and the solution is skipped. Thereafter, THF was added thereto, and the insoluble material was separated by filtration, methanol was added to solubilize the diarylethene having sodium ions, and crystals were taken out from the filtrate by recrystallization.

The presence of sodium ions in the crystals was confirmed by IR and MASS spectra.
That is, 2500-3300 cm ^-1 derived from the carboxyl group
And 1700 cm ^-1 disappeared, and the absorption by the carboxylate anion was reduced to 1550-1650 cm ^-1 and 1400 cm ^-1.
cm- ¹ . According to the MASS spectrum, 65
A parent ion peak of 2 of this compound was observed.

The crystals were colored blue by irradiation with ultraviolet light and faded by irradiation with visible light. For the carboxylic acid, the absorption maximum position of the colored body is 590 in the methanol solution.
The wavelength was 610 nm for the crystal and 610 nm for the crystal, but when sodium ions were included, the wavelength was shifted to 580 nm for the methanol solution (see FIG. 1) and to 590 nm for the crystal. When the case where the alkali metal ion was not contained was compared with the case where the alkali metal ion was contained, it was recognized that the surface hardness was improved by the alkali metal ion. This is an atomic force microscope (AFM)
This was confirmed by comparison with the change in the crystal surface shape of the free acid due to the above.

1,2-bis (2-methyl-5- (4-carboxyphenyl) -thiophen-3-yl) perfluorocyclopentene (1,2-bis (2-methyl-5- (4-carboxy
phenyl) -thiophen-3-y1) perfluorocyclopentene)
It can be manufactured by the following method. (1) 2-methyl-3-bromo-5- (dihydroxyboryl) thiophene (13.0 g, 0.1 g) prepared by a conventional method.
058 mol), P-iodoacetophenone (11.3 g, 0.047 mol) and Pd (PPh ₃ ) ₄ 2.7 g were dissolved in 2N aqueous sodium carbonate solution and 500 ml of tetrahydrofuran (THF).
The mixture was refluxed under stirring for 30 minutes. Then cool to room temperature,
After post-treatment, the residue was subjected to column chromatography with silica gel to obtain 16.5 g of a condensate (yield: 96.7%). (2) 2.5 g (0.0085 mol) of the obtained condensate was
0 ml, and p-toluene sulfonic acid 25 mg and ethylene glycol 5.8 g (0.093 mol) were added thereto.
Refluxed for hours. 2.8 of the desired ethylenedioxyketal
g (97.2% yield).

(3) 2.8 g (0.0083 mol) of the obtained ethylenedioxyketal was dissolved in 220 ml of dry THF, and
Cooled to 8 ° C. Here, n-BuLi 5.53 ml (0.0
091 mol) was slowly added dropwise. After 25 minutes, 0.55 ml (0.0041 mol) of perfluorocyclopentene was added in three portions. After maintaining at -78 ° C for 2 hours, the reaction was stopped with a small amount of methanol. To remove the protective group ketal, hydrochloric acid was added and the mixture was stirred overnight. This was treated and separated on a silica gel chloroform column, and 750 mg of 1,2-bis (2-methyl-5- (4-acetylphenyl) -thiophen-3-yl) perfluorocyclopentene was obtained (yield: 3).
0.0%). (4) The obtained acetyl compound (400 mg, 0.66 mmol) was dissolved in dioxane (60 ml) and the mixture was allowed to stand at 55 ° C. for 30 minutes. there,
NaOCI (10 ml) was slowly added dropwise, and the mixture was stirred at 80 ° C for 2 hours. This was treated and 350 mg (yield: 87.2%) of the desired carboxylic acid derivative was obtained by a reprecipitation method.

Example 2 1,2-bis (2-methyl-5- (4-carboxyphenyl) thiophene-3 containing potassium and cesium ions
-Yl) perfluorocyclopentene was prepared in the same manner as in Example 1. These crystals were also colored blue by irradiation with ultraviolet light and faded by irradiation with visible light, similarly to the case where sodium ions were included. The absorption maximum position of the colored body was observed at 582 nm for potassium ions and at 578 nm for cesium ions. Also in these, improvement of hardness was recognized.

Example 3 By the same method as described in Example 1, the following diarylethene compound having a sodium ion can be produced. These crystals are similarly colored blue by irradiation with ultraviolet light, fade by irradiation with visible light, and have higher surface hardness than compounds having a free ionic substituent having no sodium ion.

1- (2-methyl-5-phenyl-3-thienyl) -2- [2-methyl-5- (4-carboxyphenyl) -3-thienyl] perfluorocyclopentene.

1- [2-methyl-5- (4-carboxyphenyl) -3-thienyl] -2- [5-methyl-2-
(4-carboxyphenyl) -4-thiazolyl] perfluorocyclopentene.

1,2-bis [5-methyl-2- (4-carboxyphenyl) -4-thiazolyl] perfluorocyclopentene.

1,2-bis [3-methyl-5- (4-carboxyphenyl) -2-thienyl] perfluorocyclopentene.

[0063]

The diheteroarylethene salt compound having at least one ionic substituent in the heteroaryl moiety changes its color upon irradiation with light, and returns to its original state when irradiated with light of another wavelength. Has properties. If such a salt compound of diheteroarylethene is used as a photochromic crystal material, a high-sensitivity, high-durability photoresponsive functional material can be prepared.If a single crystal is formed from this material, a hard and durable photochromic material family can be obtained. Become. Further, it is possible to provide an optical recording material capable of performing high-performance reversible recording in a photon mode.

[Brief description of the drawings]

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 shows 1,2-bis (2-methyl-5- (4
3 shows the absorption spectrum of -carboxyphenyl) thiophen-3-yl) perfluorocyclopentene sodium salt in the visible region. Numerical values on the horizontal axis indicate wavelengths (nm).

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI G02F 1/17 G03C 1/73 503 1/19 G11B 7/24 501Z G03C 1/73 503 516 G11B 7/24 501 C07D 277/30 516 (58) Field surveyed (Int. Cl. ⁷ , DB name) C07D 333/24 C07D 277/20 C07D 277/30 C07D 417/08 CA (STN) REGISTRY (STN)

Claims (8)

(57) [Claims] 1. The following general formula (I): [ Wherein A and B may be the same or different from each other, and each is independently a general formula (II) of the following formula: (Wherein Y is an oxygen atom, a sulfur atom, a selenium atom or N
Represents -R ^4, W is a nitrogen atom or an ^{C-R 5,} and ^{R 1, R 2, R 3} , R 5 is each independently the same or different, bond to perfluoro-pentene ring, hydrogen Atom, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted cycloalkenyl group,
Substituted or unsubstituted heterocyclic group, substituted or unsubstituted aralkyl group, substituted or unsubstituted alkoxyl group, halogen atom, trifluoromethyl group, cyano group,
Or a substituted or unsubstituted aryl group, or ^two adjacent R ¹ , R ² , R ³ , and R ⁵ bonded together to form a substituent, Often represents a saturated or unsaturated alkylene group or alkenylene group in which at least one carbon atom in the chain may be replaced by a heteroatom, and R ⁴ represents a hydrogen atom, a substituted or unsubstituted alkyl group,
Represents a substituted or unsubstituted cycloalkyl group or a substituted or unsubstituted aryl group. However, R ¹ , R ² ,
At least one of R ³ and R ⁵ is a bond to a perfluoropentene ring, and the heterocyclic group of the general formula (II) is bonded to the perfluoropentene ring of the general formula (I). ^{Three of} R ¹ , R ² , R ³ , and R ⁵ are not simultaneously hydrogen atoms, and the remaining R ¹ , R ² , R
^3, at least one of the three groups of ^{R 5} may,
Carboxylate anion, sulfonate anion, phosphate anion
ON, pyridinium cation or quaternary ammonium cation
An aryl group substituted with an ionic substituent and composed of an ion and a counter ion of these ions . ) Represents a heterocyclic group. And a solvate thereof having at least one ionic substituent in the heterocyclic group represented by the formula: 2. The diheteroarylethene compound according to claim 1, wherein the counter ion is an alkali metal cation, an alkaline earth metal cation, an organic base cation, a halogen anion, PF ₆ ⁻ or an organic acid anion. Solvate. 3. A position adjacent to a position where the groups A and B in the general formula (I) are bonded to the perfluorocyclopentene ring of the group represented by the general formula (II), and a group represented by the general formula (I) The diheteroarylethene compound and a solvate thereof according to claim 1 or 2, wherein the position at which the compound is cyclized by receiving light is a group other than a hydrogen atom. 4. The dihetero according to claim 1, wherein the group represented by formula (II) is a 2-ionic group-substituted aryl-5-substituted-thiophen-4-yl group. Arylethene compounds and solvates thereof. 5. The dihetero according to claim 1, wherein the group represented by the general formula (II) is a 2-ionic group-substituted aryl-5-substituted-thiazol-4-yl group. Arylethene compounds and solvates thereof. 6. A photochromic crystal material comprising the diheteroarylethene compound or a solvate thereof according to claim 1. 7. An optical functional electronic device comprising the photochromic crystal material according to claim 7. 8. The optical functional electronic device according to claim 7, wherein the optical functional electronic device is an optical switch or an optical memory.