Synthesis and Properties of Non-planar Extended Quinonoid Molecules Aimed for Molecular-switching Function

用于分子开关功能的非平面延伸醌类分子的合成与性能

• 批准号: 13640534
• 负责人: KURATA Hiroyuki
• 金额: $ 2.56万
• 依托单位: Osaka University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-13640534/
• 关键词: Extended Conjugated System; Quinone; Switching; Redox System; Diradical; Photo-isomerization; ESR; Cyclic Voltammetry; ESRスペクトル; 分子不斉; キノメチド

Our research results are summarized as follows.1. Synthesis and properties of various non-planar dibenzoannetated terphenoquinonesIn order to study substituent effect on the switching process, we have synthesized a number of non-planar dibenzoannelated 3,3",5,5"-tetra-t-butylterphenoquinone derivatives. The most notable feature is the stabilization of the diradical structure of the 1,8-dimethoxy derivative.2. Synthesis and Properties of benz[d,e]anthracenylidene-p-quinone methidesWe studied the synthesis and properties of two non-planar p-quinone methides, 6H- and 7H-benz[d,e]anthracenyilidene p-quinone methides. The 6H-isomer is deep purple crystals which shows slight solvatochromism, whereas the 7H-isomer is orange crystals, indicating no solvent effect. The rotation of central double bond in 7H-isomer is observed at room temperature.3. Synthesis and properties of non-planar quinonoid compounds having 1,2-diketone structureA dibenzo-ortho-terphenoquinone derivative, the first o-terquinone derivative, is largely deviated from coplanarity, is in a slight equilibrium with its diradical form, displays an easy rotation of the exocyclic double bonds, and shows photo-responsive switching property traceable by ESR spectroscopy.

本文的研究成果概括如下：1.研究成果。各种非平面二苯并三苯二酚的合成与性质为了研究取代基对开关过程的影响，我们合成了一系列非平面二苯二苯甲酸酯3，3“，5，5”-四叔丁基四苯二酚衍生物。最显著的特征是1，8-二甲氧基衍生物的双基结构稳定。苯并[d，e]苯并[d，e]对苯二酚甲醚的合成与性质研究了两种非平面对苯二酚甲醚6H-和7H-苯并[d，e]对苯亚胺对苯二酚的合成及性质。6H-异构体为深紫色晶体，有轻微的溶致变色，而7H-异构体为橙色晶体，无溶剂效应。在室温下观察到7H-异构体中心双键的转动。具有1，2-二酮结构的二苯并邻三苯二酚类非平面化合物的合成与性质，它是第一个邻三苯二酚类化合物，与其双自由基形式的共面性有很大偏离，与其双自由基形式略有平衡，外环双键容易旋转，具有ESR谱可追踪的光响应开关性质。

项目成果

Hiroyuki Kurata: "Synthesis, Structure and Properties of a Dibenzo-ortho-terphenoquinone. The First o-Terphenoquinone Derivative"Chemistry Letters. 32. (2003)

Hiroyuki Kurata：“二苯并邻三苯醌的合成、结构和性质。第一个邻三苯醌衍生物”化学快报。

Hiroyuki Kurata: "Synthesis, Structure and Properties of a Dibenzo-ortho-terphenoquinone. The First o-Teiphenoquinone Derivative"Chemistry Letters. 32 (in press). (2003)

Hiroyuki Kurata：“二苯并邻三苯醌的合成、结构和性质。第一个邻三苯醌衍生物”化学快报。