Synthesis and Properties of Organic Donors and Acceptors making Organic Superconductor

尝试了以有机超导体为目标的新型有机供体和受体的合成及其导体的表征。开发了利用有机铝试剂合成TTF（四硫代fulvalene）衍生物的新路线，并制备了几种新的TTF衍生物。合成了以四硫戊二烯为中心的新给体，并对其结构和物理性质进行了研究。(1) TMEO-TTP一侧为甲基硫基，另一侧为乙烯二氧基，与八面体和四面体阴离子形成金属盐。(2) TTM-TTP两侧都有甲基硫基，形成3个I3盐。其中一种是金属成分，而不是1:1成分，具有一维柱状结构。其中一种2:1盐在20k以下是金属的。(3) EDT-TTP一侧被乙二硫基取代，另一侧未被取代，在室温下生成许多金属盐。(4)未取代BDT-TTP的摩尔盐在低温下具有金属性，不受反阴离子的影响。这些盐具有所谓的β型结构，金属态稳定是因为柱间相互作用是柱内相互作用的三分之一到四分之一。这些结果表明，TTF骨架的延伸有效地稳定了有机导体的金属态。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.