Ueda Akira, Hatakeyama Akari, Enomoto Masaya, Kumai Reiji, Murakami Youichi, Mori Hatsumi
The Institute for Solid State Physics, The University of Tokyo, Kashiwa, Chiba 277-8581 (Japan).
Department of Chemistry, Faculty of Science Division I, Tokyo University of Science, Shinjuku-ku, Tokyo 162-8601 (Japan).
Chemistry. 2015 Oct 12;21(42):15020-8. doi: 10.1002/chem.201502047. Epub 2015 Aug 27.
New important aspects of the hydrogen-bond (H-bond)-dynamics-based switching of electrical conductivity and magnetism in an H-bonded, purely organic conductor crystal have been discovered by modulating its tetrathiafulvalene (TTF)-based molecular π-electron system by means of partial sulfur/selenium substitution. The prepared selenium analogue also showed a similar type of phase transition, induced by H-bonded deuterium transfer followed by electron transfer between the H-bonded TTF skeletons, and the resulting switching of the physical properties; however, subtle but critical differences due to sulfur/selenium substitution were detected in the electronic structure, phase transition nature, and switching function. A molecular-level discussion based on the crystal structures shows that this chemical modification of the TTF skeleton influences not only its own π-electronic structure and π-π interactions within the conducting layer, but also the H-bond dynamics between the TTF π skeletons in the neighboring layers, which enables modulation of the interplay between the H-bond and π electrons to cause such differences.
通过部分硫/硒取代来调节基于四硫富瓦烯（TTF）的分子π电子体系，在一种氢键连接的纯有机导体晶体中发现了基于氢键（H键）动力学的电导率和磁性开关的新的重要方面。制备的硒类似物也表现出类似类型的相变，该相变由氢键连接的氘转移以及随后氢键连接的TTF骨架之间的电子转移诱导产生，并导致物理性质的开关效应；然而，在电子结构、相变性质和开关功能方面检测到了由于硫/硒取代引起的细微但关键的差异。基于晶体结构的分子水平讨论表明，TTF骨架的这种化学修饰不仅影响其自身的π电子结构和导电层内的π-π相互作用，还影响相邻层中TTFπ骨架之间的氢键动力学，这使得能够调节氢键和π电子之间的相互作用以产生此类差异。
