Rational Construction of Molecular Electron-Conducting Nanowires Encapsulated in a Proton-Conducting Matrix in a Charge Transfer Salt

Insulated molecular wires have gained significant attention owing to their potential contribution in the fields of nanoelectronics and low-dimensional chemistry/physics. Based on molecular charge transfer salts, we demonstrate, for the first time, the rational construction of molecular electron-conducting wires encapsulated in a proton-conducting matrix, which possibly paves the way to ionoelectronics. As expected from the molecular structure of the newly designed complex anion (i.e., propeller-shaped structure with hydrogen-bonding sites at four edges), a three-dimensional hydrogen-bonded framework was constructed within the crystal, which contains a one-dimensional array of an electron donor, tetrathiafulvalene (TTF). From the single-crystal crystallographic and spectroscopic studies, it was clarified that the nonstoichiometric deprotonation of anions and partial oxidation of TTFs occur, whereas the anion is electronically inert. Moderate conductivities of electron and proton were confirmed by dc and ac conductivity measurements. In addition, the electronic isolation of TTF wires was confirmed by the magnetic susceptibility data.