Synthesis and Properties of Organic Donors and Acceptors making Organic Superconductor

针对有机超导体合成了新的有机施主和受体，并对其导电性进行了表征。提出了用有机铝试剂合成四硫富瓦烯衍生物的新路线，合成了几种新的四硫富瓦烯衍生物。合成了一系列以四硫戊烯为中心的新型施主化合物，并对其结构和物理性能进行了研究。(1)TMEO-TTP的一侧为甲硫基，另一侧为乙二氧基团，与八面体和四面体阴离子形成金属盐。(2)TTM-TTP两侧均含有甲硫基，形成三种I3盐。其中一种是一维柱状结构，它不是1：1组成，而是金属结构。其中一种2：1的盐是金属的，最低温度可达20K。(3)EDT-TTP在室温下生成了许多金属盐，其一侧被亚乙二硫基取代，另一侧未被取代。(4)未取代的BDT-TTP的MOSE盐在低温下是金属的，与反阴离子无关。这些盐具有所谓的β-型结构，由于柱间相互作用高达柱内相互作用的三分之一到四分之一，金属状态是稳定的。这些结果表明，TTF骨架的扩展有效地稳定了有机导体的金属状态。取代基和阴离子的其他可能性正在调查中。

Synthesis of new organic donors and acceptors aimed toward organic superconductors, and characterization of their conductors are attempted.1. New synthesis route of TTF(tetrathiafulvalene) derivatives using organoaluminium reagents is developed, and several new TTF derivatives are prepared.2. A number of new donors where tetrathiapentalene is inserted into the center of TTF, are synthesized, and its structuers and physical properties are investigated. (1) TMEO-TTP, which has methylthio moieties on one side and an ethylenedioxy group on another side, formed metallic salts with octahedral and tetrahedral anions. (2) TTM-TTP, which has methylthio groups on both sides, formed three I3 salts. One of them, which is metallic instead of 1 : 1 composition, has one-dimensional columnar structure. One of the 2 : 1 salts is metallic down to 20 K.(3) EDT-TTP, which is substituted by an ethylenedithio group on one side and unsubstituted on another side, gave many metallic salts at room temperature. (4) Mose salts of unsubstituted BDT-TTP are metallic down to low temperatures independently of the counter anions. These salts have so-called beta-typestructure, and the metallic states are stablized because intercolumnar interaction is as large as one third to one fourth of the intracolumnar interaction.These results show that the extension of the TTF skeleton effectively stabilizes the metallic states of the organic conductors. Other possiblities of substituents and anions are under investigation.