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

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.