Construction of Redox-type Photochromic Systems Based on Photoinduced Electron Transfer Reactions in Crystalline State

基于晶态光致电子转移反应的氧化还原型光致变色体系的构建

• 批准号: 08640664
• 负责人: SUZUKI Takanori
• 金额: $ 1.22万
• 依托单位: Hokkaido University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1996
• 资助国家: 日本
• 起止时间: 1996 至 1997
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-08640664/
• 关键词: Photochromism ;; Electrochromism ;; Redox System ;; Triarylmethane; Hexaphenylethane; Molecular Device ;; Bistability ;; Functionalized Dye; ホトクロミズム; 酸化還元系; 動的酸化還元; 有機結晶; 光誘起電子移動; 固相反応

The research project is intended to construct the novel redox-type photochromic systems based on the photoinduced electron transfer reactions of electron-donor-acceptor complexes in the crystalline state. In order to realize such an idea it is essential to develop a new type of redox molecules exhibiting bistability. Thus, the redox pairs were designed so as to undergo reversible C-C bond formation and cleavage upon electron transfer. The research started from examining the interconversion hexaphenylethane derivatives 1 and dicationic bis (triarylmethane) dyes 2. It has been found that they constitute the dynamic and reversible redox pair showing vivid change in color and drastic structural change upon electron transfer. They surely are the promising candidate for the present purpose. Unfortunately, however, attempts to obtain the CT crystal of 1 with a variety of electron donors have been unsuccessful, preventing me from realizing my initial proposal. Next, the biphenyl-type electron acceptors having dicyanovinyl moieties were investigated. 2,2'-Disubstituted derivative was found to undergo C-C bond formation upon two-electron reduction. By combining the further isomerization of the reduction product, the latter system constitute a prototype of the novel electrochromic system with "write protect" option.

本研究基于电子供体受体络合物在结晶态的光致电子转移反应，构建新型氧化还原型光致变色体系。为了实现这一设想，开发一种具有双稳性能的新型氧化还原分子是非常必要的。因此，氧化还原对被设计成在电子转移时经历可逆的C-C键形成和断裂。研究从六苯乙烷衍生物1和阳离子双(三芳基甲烷)染料2的相互转化入手，发现它们构成了动态可逆的氧化还原对，在电子转移时表现出鲜明的颜色变化和剧烈的结构变化。就目前的目的而言，他们肯定是最有希望的候选人。然而，不幸的是，用各种电子给体获得1的CT晶体的尝试都没有成功，使我无法实现我最初的建议。其次，研究了具有双氰基的联苯型电子受体。发现2，2‘-二取代衍生物在两电子还原时形成C-C键。通过结合还原产物的进一步异构化，后者系统构成了具有写保护选项的新型电致变色系统的原型。

项目成果

Takanori, Suzuki: "Hexaphenylethane Derivatives Bxhibiting Novel Electrochromic Behavior" Angew.Chem.Int.Ed.Engl. 36・12. 1329-1331 (1997)

Takanori, Suzuki：“六苯乙烷衍生物表现出新颖的电致变色行为”Angew.Chem.Int.Ed.Engl. 1329-1331 (1997)

T.Suzuki: "Photoreactions of Crystalline Charge-Transfer Complexes" Pure Appl.Chem.68. 281-284 (1996)

T.Suzuki：“晶体电荷转移复合物的光反应”Pure Appl.Chem.68。

T. Suzuki: "Tetracyanoquinodime thanes fused with a 〔1,2,5〕Chalcogena diazole Ring" Mol. Cryst. Liq. Cryst.(印刷中). (1997)

T. Suzuki：“与[1,2,5]硫属二唑环稠合的四氰基喹啉”晶体。（1997 年出版）。

Hidetoshi, Kawai: "Kinetically Stabillized[1.1]Paracyclophane.Isolation and X-ray Structural Analysis" Angew.Chem.Int.Ed.Engl. 37・-(in press). (1998)

Hidetoshi, Kawai：“Kinetically Stabilized[1.1]Paracyclophane.Isolation and X-ray Structural Analysis”Angew.Chem.Int.Ed.Engl. 37・-（印刷中）。

T.Tsuji: "Tricyclo [4.2.2.22,5] dodeca-1,3,5,7,9,11-hexaene : generation and chemical trapping of the 3,4-dicyano derivative" J.Chem.Soc., Chem.Commun.2151-2152 (1997)

T.Tsuji：“三环[4.2.2.22,5] dodeca-1,3,5,7,9,11-己烯：3,4-二氰基衍生物的生成和化学捕获”J.Chem.Soc.，Chem