WITHDRAWN: Successive phase transitions in single-crystalline (C2H5NH3)2CuCl4 and potential of multiferroicity

Sakami, Tatsuhiro; Ohtani, Toshihiro; Matsumoto, Yasuhiro; Ochi, Daito; Xi, Xiaojuan; Kamikawa, Shuhei; Ohyama, Junpei; Ishii, Isao; Suzuki, Takashi

doi:10.1016/j.ssc.2018.02.015

Cited by 3 publications

(3 citation statements)

References 25 publications

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“…We observe broken inversion symmetry when the organic cation has an alkyl chain of at least one carbon atom. To compare, 2D MnCl 4 -based perovskites adopt centrosymmetric structures when the cation has a simple alkyl chain. − This implies that the introduction of a phenyl ring can lead to a polar structure. It is therefore useful to examine the structures of 1 – 4 in more detail to identify the mechanism by which inversion symmetry is broken.…”

Section: Resultsmentioning

confidence: 99%

Polar Structure and Two-Dimensional Heisenberg Antiferromagnetic Properties of Arylamine-Based Manganese Chloride Layered Organic–Inorganic Perovskites

et al. 2021

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The breaking of inversion symmetry can enhance the multifunctional properties of layered hybrid organic–inorganic perovskites. However, the mechanisms by which inversion symmetry can be broken are not well-understood. Here, we study a series of MnCl 4 -based 2D perovskites with arylamine cations, namely, (C 6 H 5 C x H 2 x NH 3 ) 2 MnCl 4 ( x = 0, 1, 2, 3), for which the x = 0, 1, and 3 members are reported for the first time. The compounds with x = 1, 2, and 3 adopt polar crystal structures to well above room temperature. We argue that the inversion symmetry breaking in these compounds is related to the rotational degree of freedom of the organic cations, which determine the hydrogen bonding pattern that links the organic and inorganic layers. We show that the tilting of MnCl 6 octahedra is not the primary mechanism involved in inversion symmetry breaking in these materials. All four compounds show 2D Heisenberg antiferromagnetic behavior. A ferromagnetic component develops in each case below the long-range magnetic ordering temperature of ∼42–46 K due to spin canting.

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Section: Resultsmentioning

confidence: 99%

Polar Structure and Two-Dimensional Heisenberg Antiferromagnetic Properties of Arylamine-Based Manganese Chloride Layered Organic–Inorganic Perovskites

et al. 2021

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“…Recently copper-based halide perovskites with Jahn–Teller (J–T) distortion of the 3d 9 ion Cu 2+ have been widely explored as a platform for developing new multifunctional materials due to their interesting thermochromism, ferromagnetism, and ferroelectricity. − To date, few copper-based halide perovskites with halogen-substituted organic molecule spacers have been prepared. 2D layered perovskites (CEA) 2 CuCl 4 (CEA = 2-chloroethylammonium and (BEA) 2 CuCl 4 (BEA = 2-bromoethylammonium) with chlorine and bromine substitution in ethylamine exhibit reversible and irreversible thermochromism, which can be modulated by incorporating organic cations .…”

Section: Introductionmentioning

confidence: 99%

Polar Ferromagnet Induced by Fluorine Positioning in Isomeric Layered Copper Halide Perovskites

et al. 2022

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We present the influence of positional isomerism on the crystal structure of fluorobenzylammonium copper(II) chloride perovskites A 2 CuCl 4 by incorporating ortho- , meta -, and para -fluorine substitution in the benzylamine structure. Two-dimensional (2D) polar ferromagnet (3-FbaH) 2 CuCl 4 (3-FbaH + = 3-fluorobenzylammonium) is successfully obtained, which crystallizes in a polar orthorhombic space group Pca 2 1 at room temperature. In contrast, both (2-FbaH) 2 CuCl 4 (2-FbaH + = 2-fluorobenzylammonium) and (4-FbaH) 2 CuCl 4 (4-FbaH + = 4-fluorobenzylammonium) crystallize in centrosymmetric space groups P 2 1 / c and Pnma at room temperature, respectively, displaying significant differences in crystal structures. These differences indicate that the position of the fluorine atom is a driver for the polar behavior in (3-FbaH) 2 CuCl 4 . Preliminary magnetic measurements confirm that these three perovskites possess dominant ferromagnetic interactions within the inorganic [CuCl 4 ] ∞ layers. Therefore, (3-FbaH) 2 CuCl 4 is a polar ferromagnet, with potential as a type I multiferroic. This work is expected to promote further development of high-performance 2D copper(II) halide perovskite multiferroic materials.

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“…Copper-based halide perovskites have recently been studied intensively for developing new multifunctional materials because of their interesting thermochromism, ferromagnetism, and ferroelectricity. − The Cu-based perovskites possess the inherent benefits of lower toxicity and greater light and humidity stability, in comparison to Pb-, Cd-, Sn-, or Bi-based perovskites. , Structurally, the Jahn–Teller (J–T) distortion of the 3d 9 ion Cu 2+ results in the elongation of octahedral coordination, introducing additional flexibility into copper-based systems . Consequently, more complex organic moieties can be included in copper halide perovskites to adjust the physical and chemical properties.…”

Section: Introductionmentioning

confidence: 99%

Polarity and Ferromagnetism in Two-Dimensional Hybrid Copper Perovskites with Chlorinated Aromatic Spacers

et al. 2022

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Two-dimensional (2D) organic–inorganic hybrid copper halide perovskites have drawn tremendous attention as promising multifunctional materials. Herein, by incorporating ortho -, meta -, and para -chlorine substitutions in the benzylamine structure, we first report the influence of positional isomerism on the crystal structures of chlorobenzylammonium copper(II) chloride perovskites A 2 CuCl 4 . 2D polar ferromagnets (3-ClbaH) 2 CuCl 4 and (4-ClbaH) 2 CuCl 4 (ClbaH + = chlorobenzylammonium) are successfully obtained. They both adopt a polar monoclinic space group Cc at room temperature, displaying significant differences in crystal structures. In contrast, (2-ClbaH) 2 CuCl 4 adopts a centrosymmetric space group P 2 1 / c at room temperature. This associated structural evolution successfully enhances the physical properties of the two polar compounds with high thermal stability, discernible second harmonic generation (SHG) signals, ferromagnetism, and narrow optical band gaps. These findings demonstrate that the introduction of chlorine atoms into the interlayer organic species is a powerful tool to tune crystal symmetries and physical properties, and this inspires further exploration of designing high-performance multifunctional copper-based materials.

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WITHDRAWN: Successive phase transitions in single-crystalline (C2H5NH3)2CuCl4 and potential of multiferroicity

Cited by 3 publications

References 25 publications

Polar Structure and Two-Dimensional Heisenberg Antiferromagnetic Properties of Arylamine-Based Manganese Chloride Layered Organic–Inorganic Perovskites

Polar Structure and Two-Dimensional Heisenberg Antiferromagnetic Properties of Arylamine-Based Manganese Chloride Layered Organic–Inorganic Perovskites

Polar Ferromagnet Induced by Fluorine Positioning in Isomeric Layered Copper Halide Perovskites

Polarity and Ferromagnetism in Two-Dimensional Hybrid Copper Perovskites with Chlorinated Aromatic Spacers

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