Syntheses and Properties of Tetrathiotetrathiafulvalene Derivatives of Cyclophane-Type Structures

环芬型结构四硫代四硫富瓦烯衍生物的合成及性能

基本信息

批准号：
07640706
负责人：
KAWADA Yuzo
金额：
$ 1.41万
依托单位：
IBARAKI UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
1995
资助国家：
日本
起止时间：
1995 至 1996
项目状态：
已结题

项目摘要

TTF derivatives having cyclophane structure have been proposed to realize new unique arrangements and intermolecular interactions of TTF units. Among them cross-cyclophane twin donors, in which long axs of TTF units are fixed in a cross orientation by four ethylendithio (1), trimethylenedithio (2), and trimethylenediseleno (3) chains, were successfully prepared. Intramolecular double couplings of macrocyclic dmit tetramers to give the central double bond of TTF units are most effective to obtain 1 and 2, whereas 3 was prepared starting from TTF.Although the donor ability of 1 was low due to a heavy bending of the donor units, that of 2 was the same as BEDT-TTF.The crystal structures of a charge transfer complex, 2・TCNQ,and an ion radical salt 2・Br (1,1,2-TCE) _2, revealed that 2 has an ability to construct characteristic self-assembled structures, recognizing a size and a shape of acceptors or counter ions.The almost isotropic conducting properties of the ion radical salt was interpreted based on the unique molecular structure of 2.The temperature dependence of the magnetic susceptibility of the salt revealed a basically paramagnetic nature of magnetic behavior, but it showed ferromagnetic interaction at lower temperatures.In spite of various attempts, twin donors, where long axs of TTF units are held parallel by four ethylendithio or trimethylendithio groups, are yet to be prepared. Conformation and /or orientation of the two TTF units arranged in a parallel fashion compared to cross or extended ones could be the reason.

具有环芳结构的TTF衍生物已被提出来实现TTF单元的新的独特排列和分子间相互作用，其中跨环芳双给体，其中TTF单元的长轴由四个乙二硫基(1)、三亚甲基二硫基(1)以交叉方向固定。 2）和三亚甲基二硒（3）链，成功制备大环dmit四聚体的分子内双偶联，得到TTF的中心双键。单元最有效地获得1和2，而3是从TTF开始制备的。虽然1的供体能力由于供体单元的严重弯曲而较低，但2的供体能力与BEDT-TTF相同。晶体结构电荷转移络合物 2·TCNQ 和离子自由基盐 2·Br (1,1,2-TCE) _2 的研究表明 2 具有构建特征自组装结构的能力，可识别尺寸和受体或反离子的形状。基于2的独特分子结构解释了离子自由基盐的几乎各向同性的导电性质。盐的磁化率的温度依赖性揭示了磁行为的基本顺磁性质，但它在较低温度下表现出铁磁相互作用。尽管进行了各种尝试，但尚未制备出双供体，其中TTF单元的长轴由四个乙二硫基或三亚甲基二硫基团保持平行。与交叉或延伸的相比，以平行方式排列的两个 TTF 单元的构象和/或方向可能是原因。