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.

已经提出了具有环烷结构的TTF衍生物，以实现TTF单元的新独特布置和分子间相互作用。其中包括跨环保双供体，其中四个Ethylendithio（1），Trimethylendithio（2）和Trimethylendiseleno（3）链固定在TTF单元的长轴中，成功制定了。大环的室内双重双耦合使TTF单位的中央双键具有最有效的获得1和2，而从TTF开始制备3个供体能力。尽管供体能力较低，但由于供体单位的倾斜很大，该供体的倾斜度与BEDT TTF相同。 2 ・ br（1,1,2-TCE）_2，表明2具有构造特征性自组装结构的能力，识别尺寸和受体或反离子的形状。基于2.的独特的分子依赖性，但基于盐的磁性依赖性的独特性依赖性，几乎是盐自由基盐的各向同性导电性能，但均具有基本含量的范围。在较低的温度下，在各种尝试中，双供体（双供体）尚未准备好四个乙基迪迪西奥或三甲基通道组平行的TTF单位的供体。与交叉或扩展的两个TTF单元相比，以平行方式安排的两个TTF单元的会议和 /或方向可能是原因。