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Synthesis and Properties of Novel Extended pi-Conjugated Systems with Good Functionality

具有良好功能的新型扩展π共轭体系的合成与性能

基本信息

批准号：
08454201
负责人：
ODA Masaji
金额：
$ 4.99万
依托单位：
Osaka University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
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

项目摘要

Although pi-conjugated molecules will small to medium size have been studied extensively, those with larger pi-systems have remained much to be explored and studied probably owing to increasing difficulties in the synthesis, handling, and structural characterization. The primary purpose of this project is to design, synthesize, and elucidate the structure-property relationship of novel extended pi-systems. The following results have been obtained in these two years.(1) Following to our first synthesis of several triquinarenemethane di-ions, we have succeeded in the synthesis of hexacyanotriquinarenemethane dianion 1, a stable and highly tetrapolar substance, and triquinarenemethane di-ions having aromatic ion moieties at the terminals. These di-ions show strong absorptions in the visible to near-infrared region.(2) For the synthesis of 1 we have developed a versatile synthon which is widely applicable to the synthesis of a variety of dicyanoquinodimethanes. As the first examples we synthesized and studied a number of dicyanodiarylquinodimethanes 2 whose dipolarity largely changes by the electronic nature of para-substituents.(3) Taking electron-withdrawing nature of boron atom into account, we designed and synthesized sterically protected boraquinodimethanes 3 and a triquinarenemethane analogue having a boron atom at the center. Compounds 3 show appreciable solvatoshromism and further studies are undergoing.(4) We have also synthesized dendrimer-type hexacations based on hexa-substituted benzene skeleton 4, tetrakis (2-thienyl) quinodimethanes 5, and a new dibenzoterquinone derivative 6. Compounds 4 are the first example of hydrocabon haxaxation, quinodimethanes 5 show good amphoteric redox properties, and the extended quinone 6 undergoes a highly reversible photochemical and thermal isomerization between quinone and diradical form involving conformational change. This property of 6 represents a switch function.

尽管已经对小到中等尺寸的pi共轭分子进行了广泛的研究，但由于在合成、处理和结构表征方面的困难越来越大，具有较大pi体系的pi共轭分子仍有许多有待探索和研究的地方。本课题的主要目的是设计、合成和阐明新型扩展pi系统的结构-性质关系。在这两年中取得了以下成果：(1)继我们第一次合成了几个三醌甲烷二离子之后，我们又成功地合成了六氰三醌甲烷二离子1，这是一种稳定的高度四极性物质，以及在末端具有芳香离子部分的三醌甲烷二离子。这些离子在可见光到近红外波段有很强的吸收。(2)对于1的合成，我们开发了一种广泛适用于合成多种二氰喹二甲烷的通用性合成方法。作为第一个例子，我们合成并研究了一些双氰二酰基喹二甲烷2，它们的双极性很大程度上是由对取代基的电子性质改变的。(3)考虑到硼原子的吸电子性质，设计合成了具有立体保护作用的硼喹二甲烷3和中心有硼原子的三醌甲烷类似物。化合物3表现出明显的溶剂致变色作用，进一步的研究正在进行中。(4)我们还合成了基于六取代苯骨架的树状六合物4、四（2-噻吩基）喹二甲烷5和一种新的二苯并醌衍生物6。化合物4是第一个碳氢化合物haxaxation的例子，醌二甲烷5表现出良好的两性氧化还原性质，扩展的醌6在醌和二自由基形式之间发生了高度可逆的光化学和热异构化，涉及构象变化。6的属性表示一个开关函数。