Development of new multi-color electrochromic system by use of redox-active pi conjugated compounds

利用氧化还原活性π共轭化合物开发新型多色电致变色系统

• 批准号: 63550646
• 负责人: SUGIMOTO Toyonari
• 金额: $ 1.02万
• 依托单位: KYOTO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1988
• 资助国家: 日本
• 起止时间: 1988 至 1989
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-63550646/
• 关键词: hydroxyphenylthienothiophene; 1,3-dithiole-radialene; 1,3-dithiole-dendralene; redox; electrochromism; near-infrared region absorption dye; デンドラレン; ラジアレン; 酸化還元; エレクトロクロミズム; 多色変化; 電子供与性1,3ージチオール基; チエノチオフェン

Organic compounds with multi-color change are of current interest from development of new types of display systems. This research project has been carried out with aim of developing such multi-color organic electrochromic systems by use of the following redox-active pi conjugated compounds: (1) tetrakis(2,6-di-tert-butyl-4-hydroxyphenyl)- thieno[3,2-b]thiophene (1), (2) 1,3-dithiole-[n]radialenes (n=3, 4, 5, 6) (2), and (3) 1,3-dithiole-[n]dendralenes (n=3, 4) (3). As for 1 a reversible redox system was constructed with the corresponding two- and four-electron oxidized compounds, the mono- quinone (1') and diquinone (1''). Between the three components a large color change was observed: 1 (pale yellow), 1' (blue), and 1'' (brown red). It was very surprising that 1' and 1'' have absorption maxima at fairly long wavelength region, in spite of their not so large pi conjugation. As a result of some investigations, it was suggested that the excited state (biradical structure) might be located at comparatively low energy level and the transition energy from HOMO to LUMO might become very smaller. The indirect evidence to this suggestion was obtained from the detailed esr measurement of 1' and 1'', in which certainly the biradical involvement was recognized. Also, 2 and 3 exhibited electrochromism between their radical cations and dications. In particular, a comparatively large three color change was observed between 3 (yellow), and the radical cation (dark blue) and dication (green).

具有多色变化的有机化合物是当前新型显示系统开发的关注点。该研究项目的目的是通过使用以下氧化还原活性π共轭化合物来开发这种多色有机电致变色系统：（1）tetrakis（2，6-二叔丁基-4-羟基苯基）-噻吩并[3，2-B]噻吩（1），（2）1，3-二硫杂环戊烯-[n]辐烯（n=3，4，5，6）（2）和（3）1，3-二硫杂环戊烯-[n]树状烯（n=3，4）（3）。1与相应的二电子和四电子氧化物单醌（1 ′）和二醌（1 ″）构成可逆氧化还原体系。在三种组分之间观察到较大的颜色变化：1（浅黄色）、1“（蓝色）和1”（棕红色）。非常令人惊讶的是，1'和1“在相当长的波长区域具有吸收最大值，尽管它们的π共轭不是那么大。研究结果表明，激发态（双自由基结构）可能位于较低的能级，从HOMO到LUMO的跃迁能可能变得很小。这一建议的间接证据是从1'和1“的详细ESR测量中获得的，其中肯定承认了双自由基的参与。此外，2和3表现出电致变色之间的自由基阳离子和双阳离子。特别地，在3（黄色）与自由基阳离子（深蓝色）和双阳离子（绿色）之间观察到比较大的三种颜色变化。

项目成果

Yohji Misaki: "Synthesis and Properties of 1,3-Dithiole-[3]-and-[4]-Dendralenes, Acyclic Systems of the Corresponding[3]-and[4]-Radialenes" Tetrahedron Letters. 30. 5289-5292 (1989)

Yohji Misaki：“1,3-二硫醇-[3]-和-[4]-Dendralenes的合成和性质，相应[3]-和[4]-Radialenes的无环系统”四面体字母。

Yoyonari Sugimoto: "Design of Purely Molecular/Organic Ferromagnets by Use of Odd-numbered [n]-Radialenes" Molecular Crystals and Liquid Crystals. 176. 259-270 (1989)

Yoyonari Sugimoto：“使用奇数 [n]-Radialenes 设计纯分子/有机铁磁体”分子晶体和液晶。

Toyonari Sugimoto: Angewandte Chemie,International Edition in English. 27. 1078-1080 (1988)

Toyonari Sugimoto：Angewandte Chemie，英文国际版。

Toyonari Sugimoto: Journal of the American Chemical Society. 110. 628-629 (1988)

杉本丰成：美国化学会杂志。

Toyonari Sugimoto: "Redox-Active Thieno[3,2-b]thiophene Composing of a Novel,Three-Color Electrochromic System" Angewandte Chemie International Edition in English. 27. 560-561 (1988)

Toyonari Sugimoto：“氧化还原活性噻吩并[3,2-b]噻吩组成新颖的三色电致变色系统”Angewandte Chemie 国际英文版。