JP3491704B2 - Dithienylethene compound and photochromic material comprising the compound - Google Patents
Dithienylethene compound and photochromic material comprising the compoundInfo
- Publication number
- JP3491704B2 JP3491704B2 JP25685594A JP25685594A JP3491704B2 JP 3491704 B2 JP3491704 B2 JP 3491704B2 JP 25685594 A JP25685594 A JP 25685594A JP 25685594 A JP25685594 A JP 25685594A JP 3491704 B2 JP3491704 B2 JP 3491704B2
- Authority
- JP
- Japan
- Prior art keywords
- compound
- photochromic
- formula
- irradiation
- dithienylethene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Landscapes
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
- Optical Record Carriers And Manufacture Thereof (AREA)
- Eyeglasses (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ジチエニルエテン系化
合物及びフォトクロミック材料に関する。FIELD OF THE INVENTION The present invention relates to dithienylethene compounds and photochromic materials.
【０００２】[0002]
【従来の技術】フォトクロミック材料とは、光の作用に
より状態の異なる２つの異性体を可逆的に生成する分子
または分子集合体を含む材料をいう。フォトクロミック
材料は、その光異性化に伴い光吸収係数、屈折率あるい
は誘電率を可逆的に変える。これらの光物性変化が、光
メモリ媒体あるいは光スイッチ素子などの光機能材料へ
応用されている。これらの目的のため、繰り返し耐久性
を有し、かつ熱不可逆なジアリールエテン系化合物、フ
ルギド系化合物等のフォトクロミック分子の開発が進め
られてきた。現在ジアリールエテン分子については、十
分な繰り返し耐久性、熱不可逆性を持つものが得られて
いる（Ｍ．Ｉｒｉｅ，Ｍｏｌ．Ｃｒｙｓｔ．Ｌｉｑ．Ｃ
ｒｙｓｔ．２２７，２６３（１９９３））。2. Description of the Related Art A photochromic material is a material containing a molecule or a molecular assembly which reversibly produces two isomers having different states by the action of light. The photochromic material reversibly changes its light absorption coefficient, refractive index or dielectric constant with its photoisomerization. These changes in optical properties have been applied to optical functional media such as optical memory media or optical switch elements. For these purposes, development of photochromic molecules such as diarylethene compounds and fulgide compounds, which have repeated durability and are irreversible with heat, has been advanced. At present, diarylethene molecules having sufficient cyclic durability and thermal irreversibility have been obtained (M. Irie, Mol. Cryst. Liq. C).
ryst. 227, 263 (1993)).
【０００３】[0003]
【発明が解決しようとする課題】これらの分子を光メモ
リ媒体あるいは光スイッチ素子へ応用する際には、吸光
度あるいは屈折率が光照射により大きく変化することが
要求される。しかし、これまでのフォトクロミック材料
はいずれもフォトクロミック分子を固体高分子媒体へ分
散させたものであるため、フォトクロミック分子の濃度
を上げることが困難で、十分な変化量を得ることができ
ていない問題点をもつ。When these molecules are applied to an optical memory medium or an optical switch element, it is required that the absorbance or the refractive index be largely changed by the light irradiation. However, all of the photochromic materials to date are those in which photochromic molecules are dispersed in a solid polymer medium, so it is difficult to increase the concentration of the photochromic molecules, and a sufficient amount of change cannot be obtained. With.
【０００４】[0004]
【課題を解決するための手段】吸光度あるいは屈折率を
大きく光変化させるには、２つの方法が考えられる。一
つは、分子自身の吸光係数あるいは分子屈折率を上げる
ことであり、もう一つは、高分子媒体中への分子分散濃
度を上げることである。前者の方法として、強い電子供
与基をもつ分子の合成が試みられており、２万程度の吸
光係数をもつジアリールエテン分子が報告されている
（入江、酒村、日本化学会第６７春季年会予稿集）。Two methods are conceivable for making a large light change in the absorbance or the refractive index. One is to increase the extinction coefficient or the molecular refractive index of the molecule itself, and the other is to increase the concentration of dispersed molecules in the polymer medium. As the former method, synthesis of a molecule having a strong electron-donating group has been tried, and a diarylethene molecule having an extinction coefficient of about 20,000 has been reported (Irie, Sakamura, The 67th Annual Meeting of the Chemical Society of Japan). Collection).
【０００５】本発明者は、後者の方法の究極の状態であ
る媒体を用いない系においてフォトクロミック反応する
分子について鋭意探索し、その結果、結晶状態でフォト
クロミック反応する特定の複素芳香族置換されたエテン
分子を見い出した。即ち、本発明の要旨は、下記一般式
（Ｉ）又は（ II ）の分子構造を有する、結晶状態のジチ
エニルエテン系化合物からなるフォトクロミック材料に
存する。The present inventor diligently searched for a molecule that undergoes a photochromic reaction in a medium-free system, which is the ultimate state of the latter method, and as a result, a specific heteroaromatic-substituted ethene that undergoes a photochromic reaction in a crystalline state is obtained. I found a molecule. That is, the gist of the present invention is to provide a crystalline dithiosilane having a molecular structure of the following general formula (I) or ( II )
It exists in a photochromic material composed of an enylethene compound .
【０００６】[0006]
【化２】
（０００７） （各式中、Ｒ１及びＲ４はアルキル基、
Ｒ２及びＲ５はアルキル基又は水素原子、Ｒ３及びＲ６
は水素原子又はハロゲン原子をそれぞれ独立して表
す。）また、本発明の別の要旨は、上記一般式（ II ）
で、Ｒ ３ 、Ｒ ６ が水素原子を示す構造を有するジチエニ
ルエテン系化合物に存する。以下、本発明を詳細に説明
する。フランあるいはチオフェン環をジアリールエテン
系化合物のアリール基に代えて有する化合物は、熱不可
逆性のフォトクロミック反応性を示す。最も単純なジチ
エニルエテンはジ（２，４，５−トリメチル−３−チエ
ニル）ペルフルオロシクロペンテンであり、これはフォ
トクロミック反応に伴ない下記の構造変化を起こす。[Chemical 2] (0007) (In each formula, R 1 and R 4 are alkyl groups,
R 2 and R 5 are an alkyl group or a hydrogen atom, R 3 and R 6
Represents each independently a hydrogen atom or a halogen atom. ) Further , another gist of the present invention is the above general formula ( II )
And dithieny having a structure in which R 3 and R 6 represent hydrogen atoms.
It exists in ruethene compounds. Hereinafter, the present invention will be described in detail. The compound having a furan or thiophene ring in place of the aryl group of the diarylethene compound exhibits thermo-irreversible photochromic reactivity. The simplest dithienylethene is di (2,4,5-trimethyl-3-thienyl) perfluorocyclopentene, which undergoes the following structural changes associated with the photochromic reaction.
【０００７】（各式中、Ｒ1 及びＲ4 はアルキル基、Ｒ
2 及びＲ5 はアルキル基又は水素原子、Ｒ3 及びＲ6 は
水素原子又はハロゲン原子をそれぞれ独立して表す。）
以下、本発明を詳細に説明する。フランあるいはチオフ
ェン環をジアリールエテン系化合物のアリール基に代え
て有する化合物は、熱不可逆性のフォトクロミック反応
性を示す。最も単純なジチエニルエテンはジ（２，４，
５−トリメチル−３−チエニル）ペルフルオロシクロペ
ンテンであり、これはフォトクロミック反応に伴ない下
記の構造変化を起こす。(In each formula, R 1 and R 4 are alkyl groups, R
2 and R 5 each independently represent an alkyl group or a hydrogen atom, and R 3 and R 6 each independently represent a hydrogen atom or a halogen atom. ) Hereinafter, the present invention will be described in detail. The compound having a furan or thiophene ring in place of the aryl group of the diarylethene compound exhibits thermo-irreversible photochromic reactivity. The simplest dithienylethene is di (2,4,
5-trimethyl-3-thienyl) perfluorocyclopentene, which undergoes the following structural changes associated with the photochromic reaction.
【０００８】[0008]
【化３】 [Chemical 3]
【０００９】また、これは、溶液状態ではフォトクロミ
ック反応性を示すが、結晶状態では長時間光照射しても
色変化は示さない。一方、下記式（１）及び（２）Further, although it exhibits photochromic reactivity in a solution state, it does not show a color change in the crystalline state even when it is irradiated with light for a long time. On the other hand, the following formulas (1) and (2)
【００１０】[0010]
【化４】 [Chemical 4]
【００１１】で表される化合物の白色微結晶に紫外光
（波長：２８０〜３６０ｎｍ）を照射すると結晶は赤く
なり、その赤色は可視光（波長：４７０ｎｍ以上）を照
射することにより退色した。この化合物の単結晶を作成
し、同様に紫外光、可視光照射を行ったところ、可逆的
な着色／退色反応が認められた。着色状態は、熱的に安
定であり、室温においては長時間（一週間）放置しても
退色は認められなかった。また、１００℃に昇温しても
退色は確認されなかった。即ち、この化合物は熱不可逆
性のフォトクロミック反応性を示した。When white microcrystals of the compound represented by the formula (1) were irradiated with ultraviolet light (wavelength: 280 to 360 nm), the crystals became red, and the red color was discolored by irradiation with visible light (wavelength: 470 nm or more). When a single crystal of this compound was prepared and was similarly irradiated with ultraviolet light and visible light, a reversible coloring / fading reaction was observed. The colored state was thermally stable, and no discoloration was observed even at room temperature for a long time (one week). In addition, discoloration was not confirmed even when the temperature was raised to 100 ° C. That is, this compound exhibited thermo-irreversible photochromic reactivity.
【００１２】更に、ペルフルオロシクロペンテンへの結
合位置を変えた下記式（２）で表される化合物も結晶状
態でフォトクロミック反応性を示した。この場合は、紫
外光照射により黄色く着色し、可視光照射により退色し
た。Further, a compound represented by the following formula (2) in which the bonding position to perfluorocyclopentene was changed also showed photochromic reactivity in a crystalline state. In this case, it was colored yellow by irradiation with ultraviolet light and faded by irradiation with visible light.
【００１３】[0013]
【化５】 [Chemical 5]
【００１４】本発明の一般式（Ｉ）、（II）及び（III)
において、Ｒ1 、Ｒ2 、Ｒ4 及びＲ 5 で表されるアルキ
ル基としてはメチル基、エチル基、ｎ−プロピル基、ｉ
−プロピル基、ｎ−ブチル基、ｉｓｏ−ブチル基等が挙
げられ、Ｒ3 及びＲ6 のハロゲン原子としては、フッ素
原子、塩素原子、臭素原子、ヨウ素原子が挙げられる。
これらのうち、Ｒ1 及びＲ4 としてはメチル基、Ｒ2 及
びＲ5 としてはメチル基又は水素原子、Ｒ3 及びＲ6 と
しては水素原子又はヨウ素原子が特に好ましい。更に、
Ｒ1 、Ｒ2 、Ｒ4 及びＲ5 としては、メチル基が好まし
い。本発明のジチエニルエテン系化合物は、例えば、下
記一般式（IV）、（Ｖ）、（VI）又は（VII)で表わされ
る化合物を、The general formulas (I), (II) and (III) of the present invention
Where R1, R2, RFourAnd R FiveRepresented by
As the group, methyl group, ethyl group, n-propyl group, i
-Propyl group, n-butyl group, iso-butyl group, etc.
R,3And R6The halogen atom of is fluorine
Examples include an atom, a chlorine atom, a bromine atom and an iodine atom.
Of these, R1And RFourAs a methyl group, R2Over
And RFiveIs a methyl group or hydrogen atom, R3And R6When
Especially, a hydrogen atom or an iodine atom is preferable. Furthermore,
R1, R2, RFourAnd RFiveAs a methyl group is preferred
Yes. The dithienylethene compound of the present invention is, for example,
Represented by the general formula (IV), (V), (VI) or (VII)
Compound
【００１５】[0015]
【化６】 [Chemical 6]
【００１６】（各式中、Ｒ1 、Ｒ2 、Ｒ3 、Ｒ4 、Ｒ5
及びＲ6 は前記定義と同じ。）
乾燥したテトラハイドロフランのような不活性な有機溶
媒中、低温下、好ましくは約−６０℃、ｎ−ブチルリチ
ウムのような強塩基性の化合物を添加して撹拌した後、
更にペルフルオロシクロペンテンを加え反応させること
によって製造することができる。必要に応じて、再結晶
あるいはシリカゲルカラムクロマトグラフィー等により
精製することができる。(In each formula, R 1 , R 2 , R 3 , R 4 , R 5
And R 6 are the same as defined above. ) In an inert organic solvent such as dried tetrahydrofuran, at a low temperature, preferably at about -60 ° C, after adding a strong basic compound such as n-butyllithium and stirring,
Further, it can be produced by adding and reacting perfluorocyclopentene. If necessary, it can be purified by recrystallization or silica gel column chromatography.
【００１７】本発明の化合物は、ガラス、プラスチック
板等の基板上に結晶成長させ、超薄膜を形成させること
ができる。また、本発明の化合物は、結晶状態でフォト
クロミック反応性を示すため、屈折率変化を大きくとれ
る導波路や、トランジットな偏光子がつくれるため偏光
サングラス等のフォトクロミック材料への応用が可能で
ある。The compound of the present invention can be crystal-grown on a substrate such as glass or a plastic plate to form an ultrathin film. In addition, the compound of the present invention exhibits photochromic reactivity in a crystalline state, and thus can be applied to a photochromic material such as a waveguide that allows a large change in refractive index and a transitive polarizer because it can be used as a polarized sunglasses.
【００１８】[0018]
【実施例】以下、本発明を実施例により更に詳細に説明
するが、本発明はその要旨を越えない限り、実施例によ
り限定されるものではない。
実施例１
前記式（１）で表される化合物を以下の方法で合成し
た。
（ｉ）臭素化EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to the examples as long as the gist thereof is not exceeded. Example 1 The compound represented by the above formula (1) was synthesized by the following method. (I) Bromination
【００１９】[0019]
【化７】 [Chemical 7]
【００２０】化合物（Ａ）５．０ｇ（４４．６ｍｍｏ
ｌ）を氷酢酸３００ｍｌに溶かし、０℃に冷却後、臭素
（９７．６ｍｍｏｌ）を加えて、終夜撹拌した。これを
エーテル抽出し、精製後、化合物（Ｂ）を得た（収量：
３．５ｇ）。
（ii）脱臭素化5.0 g (44.6 mmo) of compound (A)
l) was dissolved in 300 ml of glacial acetic acid, cooled to 0 ° C., bromine (97.6 mmol) was added, and the mixture was stirred overnight. This was extracted with ether and purified to obtain the compound (B) (yield:
3.5 g). (Ii) Debromination
【００２１】[0021]
【化８】 [Chemical 8]
【００２２】化合物（Ｂ）１．０ｇ（１１．８５ｍｍｏ
ｌ）を乾燥したテトラハイドロフラン５０ｍｌに溶か
し、−６０℃に冷却後、ｎ−ブチルリチウム８．６７ｍ
ｌ（１４．２ｍｍｏｌ）を加えて２時間撹拌した。次い
で、水を加えて反応を止め、エーテル抽出し、精製して
化合物（Ｃ）を得た（収量：１．０８ｇ）。
（iii)ペルフルオロシクロペンテンとのカップリング1.0 g of compound (B) (11.85 mmo)
l) was dissolved in 50 ml of dried tetrahydrofuran and cooled to -60 ° C, and then n-butyllithium 8.67m was added.
1 (14.2 mmol) was added and the mixture was stirred for 2 hours. Then, water was added to stop the reaction, the mixture was extracted with ether and purified to obtain compound (C) (yield: 1.08 g). (Iii) Coupling with perfluorocyclopentene
【００２３】[0023]
【化９】 [Chemical 9]
【００２４】化合物（Ｃ）１．００ｇ（５．５９ｍｍｏ
ｌ）を乾燥したテトラハイドロフランに溶かし、−６０
℃に冷却後、ｎ−ブチルリチウム４．１０ｍｌ（６．７
１ｍｍｏｌ）を加え、１．５時間撹拌し、その後、ペル
フルオロシクロペンテンを２時間おきに２回に分けて計
０．３２ｍｌ（２．７８ｍｍｏｌ）を加えた。溶媒を除
去後、シリカゲルカラム（溶媒：ヘキサン）カラムで精
製し、式（１）で表される化合物を６６０ｍｇ得た。1.00 g (5.59 mmo) of compound (C)
l) is dissolved in dry tetrahydrofuran and -60
After cooling to ℃, 4.10 ml of n-butyllithium (6.7
1 mmol) was added and the mixture was stirred for 1.5 hours, and then, perfluorocyclopentene was added every 2 hours in two portions to add 0.32 ml (2.78 mmol) in total. After removing the solvent, the residue was purified by a silica gel column (solvent: hexane) column to obtain 660 mg of the compound represented by the formula (1).
【００２５】得られた式（１）で表される化合物の物性
値は下記の通りであった。
融点：１３２〜１３４℃1
Ｈ−ＮＭＲδ（ＣＤＣｌ3 ）
２．０４（６Ｈ，ｓ，ＣＨ3 ２個）
２．２９（６Ｈ，ｓ，ＣＨ3 ２個）
６．７０（２Ｈ，ｓ，芳香族Ｈ ２個）
Ｍａｓｓ：Ｍ+３９６
The physical properties of the obtained compound represented by the formula (1) are as follows. Melting point: 132 to 134 ° C. 1 H-NMRδ (CDCl 3 ) 2.04 (6H, s, 2 CH 3 2) 2.29 (6H, s, 2 CH 3 2) 6.70 (2H, s, aromatic H 2 pieces Mass: M + 396
【００２６】実施例２
実施例１の方法に準じて、下記前記式（２）で表される
化合物を合成した。得られた本化合物の物性値は、下記
の通りであった。
融点：６８−７２℃1
Ｈ−ＮＭＲδ（ＣＤＣｌ3 ）
１．９７（６Ｈ，ｓ，ＣＨ3 ２個）
７．０５〜７．２０（４Ｈ，ｍ）Example 2 According to the method of Example 1, a compound represented by the following formula (2) was synthesized. The physical properties of the obtained compound were as follows. Melting point: 68-72 ° C 1 H-NMR δ (CDCl 3 ) 1.97 (6H, s, CH 3 2) 7.05 to 7.20 (4H, m)
【００２７】実施例３
実施例１の方法に準じて、前記式（３）で表される化合
物を合成した。本化合物の物性値は、下記の通りであっ
た。
融点：１３３〜１３４℃1
Ｈ−ＮＭＲδ（ＣＨＣｌ3 ）
１．７２（６Ｈ，ｓ，ＣＨ3 ２個）
２．４４（６Ｈ，ｓ，ＣＨ3 ２個）
６．５１（２Ｈ，ｓ，芳香族Ｈ ２個）
実施例４
実施例１の方法に準じて、下記一般式（４）で表される
化合物を合成した。Example 3 According to the method of Example 1, the compound represented by the above formula (3) was synthesized. The physical properties of this compound were as follows. Melting point: 133-134 ° C 1 H-NMRδ (CHCl 3 ) 1.72 (6H, s, CH 3 2) 2.44 (6H, s, CH 3 2 pieces) 6.51 (2H, s, 2 pieces aromatic H) Example 4 According to the method of Example 1, a compound represented by the following general formula (4) was synthesized.
【００２８】[0028]
【化１０】 [Chemical 10]
【００２９】本化合物の物性値は、下記の通りであっ
た。1
Ｈ−ＮＭＲδ（ＣＨＣｌ3 ）
１．７５（６Ｈ，ｓ，ＣＨ3 ２個）
２．２５（６Ｈ，ｓ，ＣＨ3 ２個）
実施例５
実施例１で合成した式（１）で表される化合物をエタノ
ールに溶解し、溶液析出法により単結晶を作成した。The physical properties of this compound were as follows: 1 H-NMR δ (CHCl 3 ) 1.75 (6H, s, CH 3 2 pieces) 2.25 (6H, s, CH 3 2 pieces) Example 5 Represented by the formula (1) synthesized in Example 1. The compound was dissolved in ethanol to prepare a single crystal by the solution precipitation method.
【００３０】[0030]
【化１１】 [Chemical 11]
【００３１】この単結晶へ紫外光（波長：３１３ｎｍ）
を照射した際の吸収スペクトルの変化を図１に照射前を
一点鎖線Ａ、照射後を実線Ｂとして示す。結晶は、赤色
に着色しその吸収極大は５３０ｎｍに観測された。この
吸収極大位置は、この化合物をヘキサンへ溶解し、紫外
光を照射した際に得られた吸収（図１の点線Ｃ）と同じ
であった。このことは、結晶中において下記のフォトク
ロミック反応が進行していることを示している。この赤
色は、可視光（波長：５３０ｎｍ）照射により退色し
た。紫外光と可視光の交互照射により、５２０ｎｍの吸
収は増減を示した（図２）。Ultraviolet light (wavelength: 313 nm) was applied to this single crystal.
The change in the absorption spectrum upon irradiation with is shown in FIG. 1 as a dot-dash line A before irradiation and as a solid line B after irradiation. The crystal was colored red and its absorption maximum was observed at 530 nm. The maximum absorption position was the same as the absorption (dotted line C in FIG. 1) obtained when the compound was dissolved in hexane and irradiated with ultraviolet light. This indicates that the following photochromic reaction is proceeding in the crystal. The red color was discolored by irradiation with visible light (wavelength: 530 nm). The absorption at 520 nm increased or decreased due to the alternating irradiation with ultraviolet light and visible light (FIG. 2).
【００３２】実施例６
実施例５で得られた単結晶を紫外光により着色させた
後、偏光顕微鏡下において偏光吸収の結晶角度依存性を
測定した。結果を図３に示す。吸収強度は、結晶と偏光
の成す角度に依存し、２つのピークを示した。これは、
ジチエニルエテンの閉環体が結晶中において２つの方向
に配向していることを示している。
実施例７
実施例２で合成した式（２）で表される化合物をエタノ
ールに溶解し、溶液析出法により単結晶を作成した。Example 6 After the single crystal obtained in Example 5 was colored with ultraviolet light, the crystal angle dependence of polarized light absorption was measured under a polarizing microscope. The results are shown in Fig. 3. The absorption intensity was dependent on the angle between the crystal and the polarized light and showed two peaks. this is,
It shows that the ring closure of dithienylethene is oriented in two directions in the crystal. Example 7 The compound represented by the formula (2) synthesized in Example 2 was dissolved in ethanol, and a single crystal was prepared by a solution precipitation method.
【００３３】[0033]
【化１２】 [Chemical 12]
【００３４】この単結晶へ紫外光（波長：３００〜４０
０ｎｍ）を照射した際の吸収スペクトルの変化を図４に
照射前を点線Ａ、照射後を実線Ｂとして示す。結晶は、
黄色に着色しその吸収極大は４２５ｎｍに観測された。
この吸収極大位置は、この化合物をヘキサンへ溶解し、
紫外光を照射した際に得られた吸収と同じであった。こ
のことは、結晶中において下記のフォトクロミック反応
が進行していることを示している。この黄色は、可視光
（波長：４１０ｎｍ以上）照射により退色した。紫外光
と可視光の交互照射により、４２５ｎｍの吸収極大は増
減を示した。Ultraviolet light (wavelength: 300 to 40) was applied to this single crystal.
(0 nm) is shown in FIG. 4 as a dotted line A before irradiation and a solid line B after irradiation. The crystals are
It was colored yellow and its absorption maximum was observed at 425 nm.
This absorption maximum position dissolves this compound in hexane,
The absorption was the same as that obtained upon irradiation with ultraviolet light. This indicates that the following photochromic reaction is proceeding in the crystal. This yellow color was discolored by irradiation with visible light (wavelength: 410 nm or more). The absorption maximum at 425 nm increased or decreased due to the alternating irradiation with ultraviolet light and visible light.
【００３５】[0035]
【発明の効果】本発明の化合物は、結晶状態でフォトク
ロミック反応性を示すため、高分子媒体へ分散させなく
とも高濃度のフォトクロミック性の薄膜を得ることがで
き、また、本発明の化合物を用いることにより高コント
ラストの導波路、偏光サングラス等フォトクロミックな
偏光材料を得ることができるため、工業上非常に有用で
ある。Since the compound of the present invention exhibits photochromic reactivity in the crystalline state, a high concentration photochromic thin film can be obtained without dispersing it in a polymer medium, and the compound of the present invention is used. As a result, a photochromic polarizing material such as a high-contrast waveguide or polarized sunglasses can be obtained, which is very useful industrially.
【図１】式（１）で表される化合物の紫外光照射による
吸収スペクトルの変化を示す図。FIG. 1 is a graph showing changes in absorption spectrum of a compound represented by formula (1) upon irradiation with ultraviolet light.
【図２】紫外光（波長：３１３ｎｍ）及び可視光（波
長：５３０ｎｍ）の交互照射による、式（１）で表され
る化合物の５２０ｎｍの吸収の変化を示す図。FIG. 2 is a diagram showing a change in absorption at 520 nm of a compound represented by formula (1) due to alternate irradiation with ultraviolet light (wavelength: 313 nm) and visible light (wavelength: 530 nm).
【図３】実施例５で得られた単結晶の５３０ｎｍの吸収
の、偏光照射による吸収強度変化を示す図。FIG. 3 is a diagram showing a change in absorption intensity at 530 nm absorption of the single crystal obtained in Example 5 upon irradiation with polarized light.
【図４】式（２）で表される化合物の紫外光照射による
吸収スペクトルの変化を示す図。FIG. 4 is a diagram showing changes in absorption spectrum of a compound represented by formula (2) upon irradiation with ultraviolet light.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｇ０２Ｆ 1/01 Ｇ０２Ｆ 1/01 Ａ 1/17 1/17 Ｇ１１Ｂ 7/24 ５１６ Ｇ１１Ｂ 7/24 ５１６ (58)調査した分野(Int.Cl.7，ＤＢ名) C07D 333/28 C07D 333/12 ＣＡ（ＳＴＮ) ＲＥＧＩＳＴＲＹ（ＳＴＮ)─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 7 Identification code FI G02F 1/01 G02F 1/01 A 1/17 1/17 G11B 7/24 516 G11B 7/24 516 (58) Fields surveyed ( Int.Cl. 7 , DB name) C07D 333/28 C07D 333/12 CA (STN) REGISTRY (STN)
Claims (2)
を有する、結晶状態のジチエニルエテン系化合物からな
るフォトクロミック材料。 【化１】 （各式中、Ｒ１、Ｒ４はアルキル基、Ｒ２、Ｒ５はアル
キル基又は水素原子、Ｒ３、Ｒ６は水素原子又はハロゲ
ン原子を示す。）1. A crystalline dithienylethene compound having a molecular structure of the following general formula (I) or ( II ) :
Photochromic material . [Chemical 1] (In each formula, R 1 and R 4 represent an alkyl group, R 2 and R 5 represent an alkyl group or a hydrogen atom, and R 3 and R 6 represent a hydrogen atom or a halogen atom.)
Ｒ ３ 、Ｒ ６ が水素原子を示す構造を有するジチエニルエ
テン系化合物。2. In the general formula ( II ) according to claim 1 ,
Dithienyl ether having a structure in which R 3 and R 6 represent hydrogen atoms
Martens compound .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25685594A JP3491704B2 (en) | 1994-10-21 | 1994-10-21 | Dithienylethene compound and photochromic material comprising the compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25685594A JP3491704B2 (en) | 1994-10-21 | 1994-10-21 | Dithienylethene compound and photochromic material comprising the compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08119963A JPH08119963A (en) | 1996-05-14 |
| JP3491704B2 true JP3491704B2 (en) | 2004-01-26 |
Family
ID=17298357
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25685594A Expired - Lifetime JP3491704B2 (en) | 1994-10-21 | 1994-10-21 | Dithienylethene compound and photochromic material comprising the compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3491704B2 (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000256663A (en) * | 1999-03-11 | 2000-09-19 | Masahiro Irie | Light-induced phase transition organic material |
| JP4533497B2 (en) * | 2000-03-24 | 2010-09-01 | コニカミノルタオプト株式会社 | Photochromic material and optical recording medium |
| US7041763B2 (en) * | 2000-07-14 | 2006-05-09 | Simon Fraser University | Photochromic polymers and methods of synthesizing same |
| CN100402526C (en) * | 2002-02-22 | 2008-07-16 | 清华大学 | Lyotropic-photochromic diarylethene and its preparation method and application |
| US7777055B2 (en) | 2002-08-09 | 2010-08-17 | Switch Materials Inc. | Photochromic and electrochromic compounds and methods of synthesizing and using same |
| DE10242435A1 (en) * | 2002-09-11 | 2004-03-25 | Heinrich-Heine-Universität Düsseldorf | Photochromic polymer compositions, useful e.g. as light protectants or data storage components, based on 1,2-bis-((hetero)aryl)-cycloalkene or bis-(cyclo(hetero)alkeno)-cyclohexa-2,6-diene derivatives |
| CN1329391C (en) * | 2003-06-13 | 2007-08-01 | 清华大学 | Organic photochromic diaryl ethylene compound and its preparation process and application |
| US7273659B2 (en) | 2003-12-18 | 2007-09-25 | Lintec Corporation | Photochromic film material |
| EP1888553A4 (en) | 2005-05-25 | 2010-03-10 | Switch Materials Inc | Photochromic and electrochromic compounds and synthesis and use thereof |
| JP5337927B2 (en) * | 2007-09-26 | 2013-11-06 | 国立大学法人兵庫教育大学 | Photochromic compound and photoreversible coloring composition |
| US9227986B2 (en) | 2011-09-30 | 2016-01-05 | Switch Materials, Inc. | Diarylethene compounds and uses thereof |
| CN113773311B (en) * | 2021-09-01 | 2023-09-26 | 岭南师范学院 | Dithiophene ethylene compound and preparation method and application thereof |
| CN115746869B (en) * | 2022-11-25 | 2024-08-06 | 华中科技大学 | A photochromic luminescent liquid crystal and its preparation method and application |
-
1994
- 1994-10-21 JP JP25685594A patent/JP3491704B2/en not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| Ｊ．Ｃｈｅｍ．Ｓｏｃ．，Ｃｈｅｍ．Ｃｏｍｍｕｎ．，（１９９４），（１８），ｐ．２１２３−４ |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08119963A (en) | 1996-05-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3491704B2 (en) | Dithienylethene compound and photochromic material comprising the compound | |
| JP4025920B2 (en) | Photochromic material | |
| WO2010061579A1 (en) | Novel crosslinked hexaaryl bisimidazole compound and derivative thereof, method for producing the compound and precursor compound to be used in the production method | |
| JPH075572B2 (en) | 2- [2- (2-hydroxyphenyl) vinylpyrazine and method for producing the same | |
| JPH08245579A (en) | Diarylethene photochromic compound and optically recording material using the compound | |
| JP2746452B2 (en) | Diarylethene compounds | |
| US5989451A (en) | Compounds and methods for doping liquid crystal hosts | |
| JP3696414B2 (en) | Photochromic crystal material | |
| US5872256A (en) | Cyclobutenedione derivative, process for preparing the same, and nonlinear optical element | |
| JP2005531629A (en) | Chiral doping agents with phenylethanediol functionality | |
| JP2006171321A (en) | Organic photorefractive material | |
| JPH0576947B2 (en) | ||
| JP2000344693A (en) | Diarylethene compound and organic photochromic film | |
| JPH06199846A (en) | Diarylethene compound | |
| JPH0413354B2 (en) | ||
| WO2000053693A1 (en) | Organic material undergoing light-induced phase transition | |
| JP2624343B2 (en) | Chromene compound and method for producing the same | |
| JPH0376785A (en) | Manufacture of photochromic material | |
| JPH0559025A (en) | Diarylethene compound | |
| KR100553514B1 (en) | Triphenodioxazine compound, preparation method thereof, use as a dichroic dye, and liquid crystal composition | |
| JP2006018113A (en) | Organic photorefractive material and optical recording material using same | |
| JPH06220048A (en) | Sulfonated diarylethene-based compound having conjugated double bond chain | |
| WO1989001181A1 (en) | Nonlinear optical material | |
| KR100647045B1 (en) | Asymmetric Dioxazine Compounds, Dichroic Dyes, Liquid Crystal Compositions and Liquid Crystal Display Devices | |
| JP2000256664A (en) | Photochromic amorphous material capable of optically controlling refractive index |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081114 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081114 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20091114 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101114 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111114 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121114 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131114 Year of fee payment: 10 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| EXPY | Cancellation because of completion of term |