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The motley family of polar compounds (MV) M(X5-xX (x)) based on anionic chains of trans-connected M-(III)(X,X)(6) octahedra (M=Bi, Sb; X, X=Cl, Br, I) and methylviologen (MV) dications

Abstract :

The search for hybrid organic-inorganic materials remains a great challenge in the field of ferroelectrics. Following the discovery of the room temperature ferroelectric material (MV)[BiI3Cl2] (MV2+: methyl-viologen) exhibiting the highest polarization value in the field of hybrid ferroelectrics, we report here nine new hybrids with the general formulation (MV)[(MX5-xX)-X-(III)(x)] (M=Bi, Sb; X, X=CI, Br, I): (MV)[BiCl3.3Br1.7] (1), (MV)[BiCl1.3Br3.7] (2), (MV)[BiBr3.2I1.8] (3), (MV)[SbCl5] (4), (MV)[SbBr5] (5), (MV)[SbCl3.8Br1.2] (6). (MV)[SbCl2.4Br2.6] (7), (MV)[SbI3Cl2] (8) and (MV)[SbBr3.8I1.2] (9). Depending on the presence of polar chains or not, and on the coupling of polar chains, two types of centrosymmetrical structures [C1] and [C2] and two types of polar structures [P1] and [P2] are defined. (2) undergoes a paraelectric-to-relaxor ferroelectric transition around 100-150 K depending of the frequency showing that the Curie temperature, T-C, of (MV)[BiBr5] (243 K) can be modulated by the substitution of Br by Cl. The most interesting family is the [P2] type because the syn coupling of polar chains is in favor of high polarization values, as in (MV)[BiI3Cl2]. Five of the nine new hybrids, (4), (6-9), which have the [P2] type structure are potential ferroelectrics. (C) 2012 Elsevier Inc. All rights reserved.

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https://hal.univ-angers.fr/hal-03344523
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Soumis le : mercredi 15 septembre 2021 - 10:07:53
Dernière modification le : jeudi 9 décembre 2021 - 15:46:06

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Nicolas Leblanc, Nicolas Mercier, Magali Allain, Oksana Toma, Pascale Auban-Senzier, et al.. The motley family of polar compounds (MV) M(X5-xX (x)) based on anionic chains of trans-connected M-(III)(X,X)(6) octahedra (M=Bi, Sb; X, X=Cl, Br, I) and methylviologen (MV) dications. Journal of Solid State Chemistry, Elsevier, 2012, 195, pp.140-148. ⟨10.1016/j.jssc.2012.03.020⟩. ⟨hal-03344523⟩

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