Role of Temperature and Pressure on the Multisensitive Multiferroic Dicyanamide Framework [TPrA][Mn(dca)3] with Perovskite-like Structure

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• 作者：Juan M. Berm煤dez-Garc铆a ; Manuel S谩nchez-And煤jar ; Susana Y谩帽ez-Vilar ; Socorro Castro-Garc铆a ; Ram贸n Artiaga ; Jorge L贸pez-Beceiro ; Luis Botana ; 脕ngel Alegr铆a ; Mar铆a A. Se帽ar铆s-Rodr铆guez
• 刊名：Inorganic Chemistry
• 出版年：2015
• 出版时间：December 21, 2015
• 年：2015
• 卷：54
• 期：24
• 页码：11680-11687
• 全文大小：458K
• ISSN：1520-510X

文摘

A multistimuli response to temperature and pressure is found in the hybrid inorganic鈥搊rganic perovskite-like [TPrA][Mn(dca)₃] compound, which is related to a first-order structural phase transition near room temperature, T_t 鈮?330 K. This phase transition involves a transformation from room temperature polymorph I, with the noncentrosymmetric space group P4虆2₁c, to the high temperature polymorph II, with the centrosymmetric space group I4/mcm, and it implies ionic displacements, order鈥揹isorder phenomena, and a large and anisotropic thermal expansion (specially along the c-axis). As a consequence, [TPrA][Mn(dca)₃] exhibits a dielectric anomaly, associated with the change from a cooperative to a noncooperative electric behavior (antiferroelectric (AFE)鈥損araelectric (PE) transition). The former implies an AFE distribution of electric dipoles in polymorph I, related to the described off-shift of the apolar TPrA cations and the order鈥揹isorder of the polar dca ligands mechanisms, that are different from those reported, up to now, for others perovskite-type hybrid compounds. Such cooperative electric order, below T_t 鈮?330 K, coexisting with long-range antiferromagnetic ordering below T = 2.1 K render the [TPrA][Mn(dca)₃] a new type-I multiferroic material. In addition, the obtained experimental results reveal that this compound is also a multistimuli-responsive material, with a very large sensitivity toward temperature and applied external pressure, 未T_t/未P 鈮?24 K kbar^鈥?, even for small values of pressure (P < 2 kbar). Therefore, this material opens up a potential interest for future technological applications, such as temperature/pressure sensing.