title: Modulation of a Molecular π-Electron System in a Purely Organic Conductor that Shows Hydrogen-Bond-Dynamics-Based Switching of Conductivity and Magnetism.
abstract: 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.
authors: The Institute for Solid State Physics, The University of Tokyo, Kashiwa, Chiba 277-8581 (Japan). a-ueda@issp.u-tokyo.ac.jp.
authors: Akira
authors: A
authors: Ueda
authors: 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).
authors: Akari
authors: A
authors: Hatakeyama
authors: Department of Chemistry, Faculty of Science Division I, Tokyo University of Science, Shinjuku-ku, Tokyo 162-8601 (Japan).
authors: Masaya
authors: M
authors: Enomoto
authors: Condensed Matter Research Center (CMRC) and Photon Factory, Institute of Materials Structure Science, High Energy Accelerator Research Organization (KEK), Tsukuba, Ibaraki 305-0801 (Japan).
authors: Reiji
authors: R
authors: Kumai
authors: Condensed Matter Research Center (CMRC) and Photon Factory, Institute of Materials Structure Science, High Energy Accelerator Research Organization (KEK), Tsukuba, Ibaraki 305-0801 (Japan).
authors: Youichi
authors: Y
authors: Murakami
authors: The Institute for Solid State Physics, The University of Tokyo, Kashiwa, Chiba 277-8581 (Japan). hmori@issp.u-tokyo.ac.jp.
authors: Hatsumi
authors: H
authors: Mori
keywords: conducting materials; electron transfer; hydrogen bonds; hydrogen transfer; phase transitions