Novel Photochromism Using Thin Films of Ion-Pair Charce-Transfer Complexes

使用离子对电荷转移络合物薄膜的新型光致变色

• 批准号: 01550629
• 负责人: NAGAMURA Toshihiko
• 金额: $ 1.28万
• 依托单位: Shizuoka University (1990)Kyushu University (1989)
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1989
• 资助国家: 日本
• 起止时间: 1989 至 1990
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-01550629/
• 关键词: Ion-Pair Charce-Transfer Complex; Polymer Films; Photochromism; Photoinduced Electron Transfer Reaction; Optical Memory; Langmuir-Blodgett Films; Polarized Absorption Spectrum; Optical Waveguide; 光レモリ-; 電荷移動錯体

The following results were obtained from the present research on novel photochromism based on the photoinduced electron transfer and thermal reverse reactions.1) Synthesis of ion-pair charge-transfer complexes4, 4'-Bipyridinium ions with symmetrical and asymmetrical substituents at 1, 1'-positions and polymers containing 4, 4'-bipyridinium ions as part of the main chain were synthesized. High bulk and chemically stable tetrakis [3,5-bis (trifluoromethyl) phenly] borate was used to form salts with 4, 4'-b-bipyridinium ions, which showed specific ion-pair charge-transfer (CT) absorption.2) Preparation of Langmuir-Blodgett films and polymer cast filmsMonolayer properties of 4, 4'-bipyridinium ions with symmetrical and asymmetrical substituents were studied in mixtures with arachidic acid. Y-type Langmuir-Blodgett (LB) films with good quality were deposited. Very thin transparent polymer films were prepared by a casting method.3) Novel photochromism upon excitation of ion-pair charge-trans … More fer bandUpon CT excitation of LB and polymer films in vacuo resulted in colour changes from pale yellow to blue due to the formation of 4, 4'-bipyridinium radical cations. The blue colour disappeared in dark reversibly with lifetimes depending on temperature and microenvironment, tau _<1/e> =4 h in LB and 72 h in polymer films at 20^ﾟC. The colour change was repeated for many times.4) Molecular control of the orientation of 4, 4'-bipyridinium radical cationsPolarized absorption spectra were measured before and after irradiation of LB films. From polarization and incident angle dependences, it was demonstrated for the first time that the molecular orientation of 4, 4'-bipyridinium radical cations was controlled by the substituents.5) Highly sensitive detection of colour changes by optical waveguide techniqueAbout 150-fold increase of sensitivity was achieved by this technique using a He-Ne laser. Colour changes in ultra thin films (about 20 nm) cast on a glass optical waveguide were successfully observed.6) Optical recording by cast films of polymeric 4, 4'-bipyridinium saltsThe lifetime of blue state in polymer films were considerably longer than in LB films. It was demonstrated that the optically written state was kept without decay below 0^ﾟC and was erased at higher temperatures. Less

1)合成了4，4‘-联吡啶离子对电荷转移络合物，合成了主链上含有对称和不对称取代基的4，4’-联吡啶离子聚合物。用高体积、化学稳定的四[3，5-二(三氟甲基)苯基]硼酸盐与4，4‘-b-联吡啶离子形成盐，表现出特殊的离子对电荷转移(CT)吸收。2)制备Langmuir-Blodgett膜和聚合物流延膜研究了具有对称和不对称取代基的4，4’-联吡啶离子在花生酸混合溶液中的单层性质。制备了质量良好的Y型Langmuir-Blodgett(LB)薄膜。采用浇铸法制备了超薄透明聚合物薄膜。3)离子对电荷传递…激发下的新型光致变色在真空中，由于4，4‘-联吡啶自由基阳离子的形成，在CT激发下，LB膜和聚合物膜的FER峰较大，导致颜色由淡黄色变为蓝色。随着温度和微环境的不同，蓝光在黑暗中可逆地消失，在20ﾟC下，T_u_t；lt；1/e&gt；=4h，在聚合物膜中为72h。4)4，4‘-联吡啶自由基阳离子取向的分子控制。从偏振和入射角的关系，首次证明了4，4‘-联吡啶自由基阳离子的分子取向受取代基的控制。5)用光波导法高灵敏地检测颜色变化。6)聚合物4，4‘-联吡啶盐浇铸膜的光记录聚合物膜的蓝态寿命明显长于LB膜。结果表明，光学写入态在0ﾟC以下没有衰变，在更高的温度下被擦除。较少

项目成果

Toshihiko Nagamura: "Control of molecular orientation 4,4'ーbipyridinium cation radicals in novel photochromic monolayer assemblies" Journal of Chemical Society,Chemical Communications. 703-704 (1990)

Toshihiko Nagamura：“新型光致变色单层组件中分子取向 4,4-联吡啶鎓阳离子自由基的控制”化学会杂志，化学通讯 703-704 (1990)。

Toshihiko Nagamura: "Persistent and reversible photoreduction of 4,4'-bipyridinium ions via excitation of their charge-transfer complexes with tetrakis[3,5-bis(trifluoromethyl)phenyl]borate in the crystalline state" Berichte der Bunsen-Gesellscahft fur ph

Toshihiko Nagamura：“通过与晶态四[3,5-双(三氟甲基)苯基]硼酸盐激发电荷转移复合物，实现 4,4-联吡啶鎓离子的持久和可逆光还原”Berichte der Bunsen-Gesellscahft Fur ph

Toshihiko Nagamura: "Photoinduced electrochromism in monolayer assemblies of charge-transfer complexes of 4, 4'-bipyridinium ions" Thin Solid Films. 179. 375-380 (1989)

Toshihiko Nagamura：“4, 4-联吡啶鎓离子电荷转移复合物单层组件中的光致电致变色”固体薄膜。

Toshihiko Nagamura: "Persistent and reversible photoreduction of 4,4'ーbipyridinium ions via excitation of their chargeーtransfer complexes with tetrakisー[3,5ーbis(trifluoromethyl)phenyl]borate in the crystalline state" Berichte der BunsenーGesellschaft fu^^‥

Toshihiko Nagamura：“通过在结晶状态下与四-[3,5-双(三氟甲基)苯基]硼酸盐激发电荷转移复合物，实现 4,4-联吡啶鎓离子的持久和可逆光还原”Berichte der Bunsen-Gesellschaft fu ^^‥

Toshihiko Nagamura: "Control of molecular orientation of 4,4'ーbipyridinium cation radicals in novel photochromic monolayer assemblies" Journal of Chemical Society,Chemical Communications. 703-704 (1990)

Toshihiko Nagamura：“新型光致变色单层组件中 4,4-联吡啶鎓阳离子自由基的分子取向控制”，《化学学会杂志》，化学通讯 703-704 (1990)。