title: Ferroelectricity and pressure-induced phenomena driven by neutral ionic valence instability of acid-base supramolecules.
abstract: Supramolecular ferroelectric cocrystals of phenazine (Phz) with chloranilic acid (H(2)ca), bromanilic acid (H(2)ba), and fluoranilic acid (H(2)fa) have been characterized by the interplay between their structural transformations and solid-state acid-base (proton transfer) reactions. At ambient pressure, the Phz-H(2)ca, Phz-H(2)ba, and their deuterated crystals exhibit incomplete proton displacement, which transforms the neutral molecules into semi-ionic at low temperatures below the Curie point (T(c)(IC) < T < T(c)(I)). For the cocrystal of the less acidic H(2)fa, the ferroelectric phase is induced only by applying hydrostatic pressure above ~0.6 GPa. According to the combined studies of temperature-dependent dielectric permittivity and synchrotron X-ray diffraction, it was proved that the ferroelectric (FE-I) phase is always accompanied at lower temperatures by successive phase transitions to the lattice modulated phases with incommensurate periodicities (IC phase, T(c)(II) < T < T(c)(IC)) and with commensurate (2- or 3-fold) periodicities (FE-II or FE-III phase, T < T(c)(II)). Whereas the ground-state structures at ambient pressure are different from one another among the Phz-H(2)ca (FE-II form), Phz-H(2)ba (FE-III form), and Phz-H(2)fa (paraelectric form), their systematic changes under pressure depict a universal pressure-temperature phase diagram. The possible origins of structural changes are assigned to the valence instability and the frustrated Coulomb interactions that induce the charge disproportionation (coexisting neutral ionic) states with the staging spatial orders.
authors.affiliation: Condensed Matter Research Center (CMRC) and Photon Factory, High Energy Accelerator Research Organization (KEK), Institute of Materials Structure Science, Tsukuba, 305-0801, Japan. reiji.kumai@kek.jp
authors.forename: Reiji
authors.initials: R
authors.lastname: Kumai
authors.forename: Sachio
authors.initials: S
authors.lastname: Horiuchi
authors.forename: Jun
authors.initials: J
authors.lastname: Fujioka
authors.forename: Yoshinori
authors.initials: Y
authors.lastname: Tokura