Ferroelectric Behavior of a Hexamethylenetetramine-Based Molecular Perovskite Structure

Hagino Morita; Ryo Tsunashima; Sadafumi Nishihara; Katsuya Inoue; Yuriko Omura; Yasutaka Suzuki; Jun Kawamata; Norihisa Hoshino; Tomoyuki Akutagawa

doi:10.1002/anie.201905087

Ferroelectric Behavior of a Hexamethylenetetramine-Based Molecular Perovskite Structure

Hagino Morita, Ryo Tsunashima, Sadafumi Nishihara, Katsuya Inoue, Yuriko Omura, Yasutaka Suzuki, Jun Kawamata, Norihisa Hoshino, Tomoyuki Akutagawa

IMRAM - Materials-Measurement Hybrid Research Center

Research output: Contribution to journal › Article › peer-review

47 Citations (Scopus)

Abstract

We report the development of a molecular ferroelectric material inspired by the hexamethylenetetramine (hmta) non-centrosymmetric molecular rotator. The bromide salt of diprotonated hmta (hmtaH₂) crystalized as (hmtaH₂)(NH₄)Br₃ in a metal-free ABX₃ perovskite-type structure, in which the A and B sites are occupied by hmtaH₂²⁺ and ammonium cations, respectively. The compound crystallized in the Pma2 polar space group. A distorted polar perovskite structure formed owing to the distortion of {(NH₄)Br₆} octahedrons that are stabilized through the formation of NH⋅⋅⋅Br hydrogen bonds and the orientational ordering of positive charges on the non-centrosymmetric hmtaH₂ molecules. This spontaneous polarization exhibited ferroelectric behavior with a nominally high Curie temperature (>400 K), in which the electrical switching of polarization originates from the rotation of the hmtaH₂ unit.

Original language	English
Pages (from-to)	9184-9187
Number of pages	4
Journal	Angewandte Chemie - International Edition
Volume	58
Issue number	27
DOIs	https://doi.org/10.1002/anie.201905087
Publication status	Published - 2019 Jul 1

Keywords

crystal engineering
ferroelectric materials
perovskite phases
solid-state structures

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title = "Ferroelectric Behavior of a Hexamethylenetetramine-Based Molecular Perovskite Structure",

abstract = "We report the development of a molecular ferroelectric material inspired by the hexamethylenetetramine (hmta) non-centrosymmetric molecular rotator. The bromide salt of diprotonated hmta (hmtaH2) crystalized as (hmtaH2)(NH4)Br3 in a metal-free ABX3 perovskite-type structure, in which the A and B sites are occupied by hmtaH22+ and ammonium cations, respectively. The compound crystallized in the Pma2 polar space group. A distorted polar perovskite structure formed owing to the distortion of {(NH4)Br6} octahedrons that are stabilized through the formation of NH⋅⋅⋅Br hydrogen bonds and the orientational ordering of positive charges on the non-centrosymmetric hmtaH2 molecules. This spontaneous polarization exhibited ferroelectric behavior with a nominally high Curie temperature (>400 K), in which the electrical switching of polarization originates from the rotation of the hmtaH2 unit.",

keywords = "crystal engineering, ferroelectric materials, perovskite phases, solid-state structures",

author = "Hagino Morita and Ryo Tsunashima and Sadafumi Nishihara and Katsuya Inoue and Yuriko Omura and Yasutaka Suzuki and Jun Kawamata and Norihisa Hoshino and Tomoyuki Akutagawa",

note = "Funding Information: We acknowledge financial support from the Opto-Energy Research Centre of Yamaguchi University, a Grant-in-Aid for Science Research from the Ministry of Education, Culture, Sports, Science, and Technology of Japan, Izumi Science and Technology Foundation, Electric Technology Research Foundation of Chugoku, and the cooperative research program of the Network Joint Research Centre for Materials and Devices of Japan. Publisher Copyright: {\textcopyright} 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",

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AU - Tsunashima, Ryo

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AU - Inoue, Katsuya

AU - Omura, Yuriko

AU - Suzuki, Yasutaka

AU - Kawamata, Jun

AU - Hoshino, Norihisa

AU - Akutagawa, Tomoyuki

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PY - 2019/7/1

Y1 - 2019/7/1

N2 - We report the development of a molecular ferroelectric material inspired by the hexamethylenetetramine (hmta) non-centrosymmetric molecular rotator. The bromide salt of diprotonated hmta (hmtaH2) crystalized as (hmtaH2)(NH4)Br3 in a metal-free ABX3 perovskite-type structure, in which the A and B sites are occupied by hmtaH22+ and ammonium cations, respectively. The compound crystallized in the Pma2 polar space group. A distorted polar perovskite structure formed owing to the distortion of {(NH4)Br6} octahedrons that are stabilized through the formation of NH⋅⋅⋅Br hydrogen bonds and the orientational ordering of positive charges on the non-centrosymmetric hmtaH2 molecules. This spontaneous polarization exhibited ferroelectric behavior with a nominally high Curie temperature (>400 K), in which the electrical switching of polarization originates from the rotation of the hmtaH2 unit.

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KW - perovskite phases

KW - solid-state structures

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Ferroelectric Behavior of a Hexamethylenetetramine-Based Molecular Perovskite Structure

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