American Chemical Society
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High-Temperature and Pressure-Induced Ferroelectricity in Hydrogen-Bonded Supramolecular Crystals of Anilic Acids and 2,3-Di(2-pyridinyl)pyrazine

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posted on 2013-03-20, 00:00 authored by Sachio Horiuchi, Reiji Kumai, Yoshinori Tokura
Cocrystallization of anilic acids (H2xa) and 2,3-di­(2-pyridinyl)­pyrazine (dppz) affords a variety of molecular geometries, including hydrogen-bonding and supramolecular structures. Proton-transferred 1:1 salts of [H-dppz]­[Hca] and [H-dppz]­[Hba] (H2ca = chloranilic acid, H2ba = bromanilic acid) were found to host room-temperature ferroelectricity with a spontaneous polarization of 3–4 μC/cm2 along the hydrogen-bonded chains. Compared with the Curie points of other supramolecular ferroelectrics, those of the salts are relatively high (402 K and >420 K, respectively) because of the elongated hydrogen bonds, which stabilize the proton-ordered state against thermal agitation. In addition to the ferroelectric black (α) form, dppz and H2ba gave two different crystal forms with a 2:3 ratio: the brown β form of [H1.5-dppz]2[Hba]3 and the brownish-red γ form of [H-dppz]2[Hba]2[H2ba]. Mixed solutions of dppz with the less acidic fluoranilic acid (H2fa) exhibit valence instability; the H2fa molecules remain mostly neutral in absolute ethanol, whereas methanol (MeOH) solution apparently increases the deprotonated Hfa content. Crystallizations of these solutions gave a neutral [dppz]­[H2fa] cocrystal and ionic [H-dppz+]­[Hfa]·MeOH salt, respectively. The ferroelectricity induced by a modest hydrostatic pressure corroborates the conclusion that the ionic state with a dipolar [H-dppz+]­[Hfa] chain is energetically close to the nonpolar neutral ground state of the [dppz]­[H2fa] crystal.