Proton dynamics and room-temperature ferroelectricity in anilate salts with a proton sponge

被引：0
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作者：
Horiuchi, Sachio [1 ]
Kumai, Reiji [1 ]
Tokunaga, Yusuke [2 ]
Tokura, Yoshinori [1 ,2 ,3 ]
机构：
[1] Correlated Electron Research Center (CERC), National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba 305-8562, Japan
[2] Tokura Multiferroics Project, ERATO, JST, Tsukuba 305-8562, Japan
[3] Department of Applied Physics, University of Tokyo, Tokyo 113-8656, Japan
来源：
Journal of the American Chemical Society | 2008年 / 130卷 / 40期
关键词：
Ferroelectricity as well as characteristic proton-transfer dynamics are achieved by combining a 2,3,5,6-tetra(2-pyridyl)pyrazine (TPPZ) molecule with anilic acids (H2xa). Dielectric measurements revealed phase transitions at Tc = 334 and 172 K for bromanilate (Hba-) and chloranilate (Hca-) salts, respectively. The room-temperature ferroelectricity of the (H2-TPPZ)(Hba)2 crystal is evidenced by the slow polarization reversal with modest pyroelectricity. In accord with the observed large deuteration effect, synchrotron X-ray diffraction studies disclosed proton dynamics in an intramolecular NH +N bond of the H2-TPPZ2+ dication and in an O-HO- hydrogen-bonded cyclic dimer of the ortho-quinoid Hxa- anions. The disordered (Hxa-)2 dimer in two-fold orientation manifests its double-proton transfer process above T c, whereas these protons are ordered in the ferroelectric phase. The H2-TPPZ2+ dication acts as a proton sponge by forming two intramolecular NH+N hydrogen bridges between the pyridyl units with a very short NN distance. The dication in the paraelectric state adopts a nonpolar geometry due to the delocalization of the protons over two sites in the respective NH+N bonds. Below Tc, only one of the two protons gets localized, and the resultant acentric H2-TPPZ2+ ion generates the dipole moment responsible for the ferroelectricity. © 2008 American Chemical Society;
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页码：13382 / 13391
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