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Function-Switchable Supramolecular System with Channel Structure

具有通道结构的功能可切换超分子系统

基本信息

批准号：
11440201
负责人：
SUGAWARA Tadashi
金额：
$ 8.96万
依托单位：
The University of Tokyo
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B).
财政年份：
1999
资助国家：
日本
起止时间：
1999 至 2000
项目状态：
已结题

项目摘要

The results obtained during the research period (1999-2000) is summarized as follows.(1) A sulfur-linked cross-cyclophane donor was found to afford a semiconductive and paramagnetic ion radical salt which exhibits a structure phase transition at 160 K.In the low-temperature phase the conductivity of the salt was increased by one-order and the number of paramagnetic spins was decreased by one-half compared with those of the high temperature phase. The phase transition turns out to be reversible and it takes place triggered by the dynamics of counter-ions and solvent molecules inside of the channel constructed in the ion radical salts. A full paper to be submitted to J.Am Chem Soc. is in preparation.(2) A selen-linked cross-cyclophane donor also afforded a semiconductive ion radical salt with a channel structure in a more organized manner. The self-assembled structure of the singly oxidized donor of the cross cyclophane shape is an excellent example which demonstrates the characteristics of a self-assembly composed of a polyhedral building block. A short communication was submitted to Chem. Communication.(3) A layer-structured ion radical salt composed of BEDT-TTF_3 Cl_2 5H_2O was discovered to exhibit a rectifying effect on the conducting property. The origin of the rectifying effect was ascribe to the current-induced translocation of counter ions assisted by the change of the hydrogen-bonding scheme in the hydrated counter ion layer. A full paper is now in preparation.

研究期间（1999-2000年）获得的结果总结如下：(1)硫链交环烷给体在160 K时产生了具有半导体顺磁性的离子自由基盐，并发生了结构相变。与高温相相比，低温相下盐的电导率提高了一个量级，顺磁自旋数减少了一半。这种相变是可逆的，它是由离子自由基盐构建的通道内的反离子和溶剂分子的动力学触发的。一篇完整的论文提交给j.a.m Chem Soc。正在准备中。(2)硒连接的交叉环烷供体也提供了具有更有组织的通道结构的半导体离子自由基盐。交叉环面形状的单氧化给体的自组装结构是一个很好的例子，它展示了由多面体组成的自组装的特征。向Chem提交了一份简短的通讯。沟通。(3)发现由BEDT-TTF_3 Cl_2 5H_2O组成的层状离子自由基盐对导电性能有整流作用。整流效应的产生是由于水合反离子层中氢键结构的改变导致了电流诱导的反离子移位。一篇完整的论文正在准备中。