Modulation of a Molecular pi-Electron System in a Purely Organic Conductor that Shows Hydrogen-Bond-Dynamics-Based Switching of Conductivity and Magnetism

作者：Ueda Akira^*; Hatakeyama Akari; Enomoto Masaya; Kumai Reiji; Murakami Youichi; Mori Hatsumi

来源：Chemistry - A European Journal, 2015, 21(42): 15020-15028.

DOI：10.1002/chem.201502047

• conducting materials
• electron transfer
• hydrogen bonds
• hydrogen transfer
• phase transitions

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 p-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 p-electronic structure and pi-pi interactions within the conducting layer, but also the H-bond dynamics between the TTF pi skeletons in the neighboring layers, which enables modulation of the interplay between the H-bond and pi electrons to cause such differences.

• 出版日期2015-10-12