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Title: The motley family of polar compounds (MV)[M(X{sub 5-x}X Prime {sub x})] based on anionic chains of trans-connected M{sup (III)}(X,X Prime ){sub 6} octahedra (M=Bi, Sb; X, X Prime =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)[BiI{sub 3}Cl{sub 2}] (MV{sup 2+}: methylviologen) exhibiting the highest polarization value in the field of hybrid ferroelectrics, we report here nine new hybrids with the general formulation (MV)[M{sup (III)}X{sub 5-x}X Prime {sub x}] (M=Bi, Sb; X, X Prime =Cl, Br, I): (MV)[BiCl{sub 3.3}Br{sub 1.7}] (1), (MV)[BiCl{sub 1.3}Br{sub 3.7}] (2), (MV)[BiBr{sub 3.2}I{sub 1.8}] (3), (MV)[SbCl{sub 5}] (4), (MV)[SbBr{sub 5}] (5), (MV)[SbCl{sub 3.8}Br{sub 1.2}] (6), (MV)[SbCl{sub 2.4}Br{sub 2.6}] (7), (MV)[SbI{sub 3}Cl{sub 2}] (8) and (MV)[SbBr{sub 3.8}I{sub 1.2}] (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{sub C}, of (MV)[BiBr{sub 5}] (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)[BiI{sub 3}Cl{sub 2}]. Five of themore » nine new hybrids, (4), (6-9), which have the [P2] type structure are potential ferroelectrics. - Graphical abstract: The methylviologen haloantimonate (MV)[SbX{sub 5-x}X Prime {sub x}] families (X, X Prime =Cl, Br, I) - [P1] and [P2] are the two kinds of polar structures - and view of the (MV)[SbBr{sub 3.8}I{sub 1.2}] hybrid based on chiral polar chains which are in syn coupling. Highlights: Black-Right-Pointing-Pointer Nine hybrids based on methylviologen and halometalate chains have been discovered. Black-Right-Pointing-Pointer The polar nature of chains is due to the ns{sup 2} stereoactivity of Sb{sup (III)} or Bi{sup (III)}. Black-Right-Pointing-Pointer A syn or anti coupling of polar chains leads to two types of polar structures. Black-Right-Pointing-Pointer Five of the nine hybrids (syn coupling) are potential interesting ferroelectrics. Black-Right-Pointing-Pointer The para-to-ferroelectric T{sub C} depends on the bromide content x of (MV)[BiCl{sub 5-x}Br{sub x}].« less

Authors:
 [1];  [1]; ;  [1]; ;  [2]
  1. Laboratoire MOLTECH-Anjou, UMR-CNRS 6200, Universite d'Angers 2 Bd Lavoisier, 49045 Angers (France)
  2. Laboratoire de Physique des Solides, UMR-CNRS 8502, Bat. 510,Universite Paris Sud, 91405 Orsay (France)
Publication Date:
OSTI Identifier:
22149897
Resource Type:
Journal Article
Journal Name:
Journal of Solid State Chemistry
Additional Journal Information:
Journal Volume: 195; Other Information: Copyright (c) 2012 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0022-4596
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; ANIONS; ANTIMONY CHLORIDES; CHAINS; ELECTRICAL PROPERTIES; FERROELECTRIC MATERIALS; HYBRIDIZATION; POLAR COMPOUNDS; POLARIZATION

Citation Formats

Leblanc, Nicolas, Mercier, Nicolas, E-mail: nicolas.mercier@univ-angers.fr, Allain, Magali, Toma, Oksana, Auban-Senzier, Pascale, and Pasquier, Claude. The motley family of polar compounds (MV)[M(X{sub 5-x}X Prime {sub x})] based on anionic chains of trans-connected M{sup (III)}(X,X Prime ){sub 6} octahedra (M=Bi, Sb; X, X Prime =Cl, Br, I) and methylviologen (MV) dications. United States: N. p., 2012. Web. doi:10.1016/J.JSSC.2012.03.020.
Leblanc, Nicolas, Mercier, Nicolas, E-mail: nicolas.mercier@univ-angers.fr, Allain, Magali, Toma, Oksana, Auban-Senzier, Pascale, & Pasquier, Claude. The motley family of polar compounds (MV)[M(X{sub 5-x}X Prime {sub x})] based on anionic chains of trans-connected M{sup (III)}(X,X Prime ){sub 6} octahedra (M=Bi, Sb; X, X Prime =Cl, Br, I) and methylviologen (MV) dications. United States. doi:10.1016/J.JSSC.2012.03.020.
Leblanc, Nicolas, Mercier, Nicolas, E-mail: nicolas.mercier@univ-angers.fr, Allain, Magali, Toma, Oksana, Auban-Senzier, Pascale, and Pasquier, Claude. Thu . "The motley family of polar compounds (MV)[M(X{sub 5-x}X Prime {sub x})] based on anionic chains of trans-connected M{sup (III)}(X,X Prime ){sub 6} octahedra (M=Bi, Sb; X, X Prime =Cl, Br, I) and methylviologen (MV) dications". United States. doi:10.1016/J.JSSC.2012.03.020.
@article{osti_22149897,
title = {The motley family of polar compounds (MV)[M(X{sub 5-x}X Prime {sub x})] based on anionic chains of trans-connected M{sup (III)}(X,X Prime ){sub 6} octahedra (M=Bi, Sb; X, X Prime =Cl, Br, I) and methylviologen (MV) dications},
author = {Leblanc, Nicolas and Mercier, Nicolas, E-mail: nicolas.mercier@univ-angers.fr and Allain, Magali and Toma, Oksana and Auban-Senzier, Pascale and Pasquier, Claude},
abstractNote = {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)[BiI{sub 3}Cl{sub 2}] (MV{sup 2+}: methylviologen) exhibiting the highest polarization value in the field of hybrid ferroelectrics, we report here nine new hybrids with the general formulation (MV)[M{sup (III)}X{sub 5-x}X Prime {sub x}] (M=Bi, Sb; X, X Prime =Cl, Br, I): (MV)[BiCl{sub 3.3}Br{sub 1.7}] (1), (MV)[BiCl{sub 1.3}Br{sub 3.7}] (2), (MV)[BiBr{sub 3.2}I{sub 1.8}] (3), (MV)[SbCl{sub 5}] (4), (MV)[SbBr{sub 5}] (5), (MV)[SbCl{sub 3.8}Br{sub 1.2}] (6), (MV)[SbCl{sub 2.4}Br{sub 2.6}] (7), (MV)[SbI{sub 3}Cl{sub 2}] (8) and (MV)[SbBr{sub 3.8}I{sub 1.2}] (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{sub C}, of (MV)[BiBr{sub 5}] (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)[BiI{sub 3}Cl{sub 2}]. Five of the nine new hybrids, (4), (6-9), which have the [P2] type structure are potential ferroelectrics. - Graphical abstract: The methylviologen haloantimonate (MV)[SbX{sub 5-x}X Prime {sub x}] families (X, X Prime =Cl, Br, I) - [P1] and [P2] are the two kinds of polar structures - and view of the (MV)[SbBr{sub 3.8}I{sub 1.2}] hybrid based on chiral polar chains which are in syn coupling. Highlights: Black-Right-Pointing-Pointer Nine hybrids based on methylviologen and halometalate chains have been discovered. Black-Right-Pointing-Pointer The polar nature of chains is due to the ns{sup 2} stereoactivity of Sb{sup (III)} or Bi{sup (III)}. Black-Right-Pointing-Pointer A syn or anti coupling of polar chains leads to two types of polar structures. Black-Right-Pointing-Pointer Five of the nine hybrids (syn coupling) are potential interesting ferroelectrics. Black-Right-Pointing-Pointer The para-to-ferroelectric T{sub C} depends on the bromide content x of (MV)[BiCl{sub 5-x}Br{sub x}].},
doi = {10.1016/J.JSSC.2012.03.020},
journal = {Journal of Solid State Chemistry},
issn = {0022-4596},
number = ,
volume = 195,
place = {United States},
year = {2012},
month = {11}
}