Syntheses and Properties of Tetrathiotetrathiafulvalene Derivatives of Cyclophane-Type Structures

TTF衍生物已提议使用全环phane结构来实现新的独特安排和TTF单元的间分子交互。在它们之间的交叉环phane双捐助者中，TTF单元的长轴固定在四个甲基（1）、三甲基化（2）和三甲基化（3）链中，准备得很好。大循环除尘器的内分子双接头给TTF单元的中央双接头是最有效的，因为1和2，3是准备好从TTF开始的，1的捐款能力低到捐赠单元的沉重弯曲，其中2个与BEDT-TTF相同。电荷转移复合体的晶体结构， 2·TCNQ，以及一个激进盐2·Br（1，1，2-TCE） _2，揭示了这2具有构建特征自组装结构的能力、识别接受者或计数器的大小和形状。离子基盐的几乎同样行为的性质是以2的独特分子结构为基础的。盐的磁性可行性的温度依赖性被揭示了一个基本的超磁性性质的磁性行为的磁性特性，但它在较低的温度下展示了铁磁相互作用，在不同的攻击、双捐助者的情况下，TTF单元的长轴由四个乙基或三甲基endithio组支撑，但仍有待准备。两个TTF单元的结构和/或方向被排列在平行时尚中，以比较交叉或扩展的单元可能是原因。

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.