Crystallographic and dielectric studies of tetrahedral {NH4@Fe4} crystallized with halomethane molecules

Daiki Matsumoto; Chiaki Tanaka; Masaru Fujibayashi; Sadafumi Nishihara; Kiyonori Takahashi; Takayoshi Nakamura; Tomoyuki Akutagawa; Atsuko Masuya-Suzuki; Ryo Tsunashima

doi:10.1039/D3CE00429E

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Crystallographic and dielectric studies of tetrahedral {NH₄@Fe₄} crystallized with halomethane molecules†

Daiki Matsumoto,^a Chiaki Tanaka,^a Masaru Fujibayashi,

^b Sadafumi Nishihara,^b Kiyonori Takahashi,

^c Takayoshi Nakamura,^c Tomoyuki Akutagawa,

^d Atsuko Masuya-Suzuki

^a and Ryo Tsunashima

*^a

Author affiliations

* Corresponding authors

^a Graduate School of Sciences and Technology for Innovation, Yamaguchi University, Yoshida 1677-1, Yamaguchi, Japan
E-mail: ryotsuna@yamaguchi-u.ac.jp

^b Graduate School of Advanced Science and Engineering, Hiroshima University, Higashi-Hiroshima 739-8526, Japan

^c Research Institute for Electronic Science, Hokkaido University, Sapporo 0010020, Japan

^d Institute of Multidisciplinary Research for Advanced Materials (IMRAM), Tohoku University, Sendai, Japan

Abstract

Crystal structures of a tetrahedral Fe₄ cluster (NH₄@Fe₄ ≡ 1) were investigated using a set of crystals prepared by changing the halomethane (CCl₄, CHCl₃, CHBr₃, CH₂Cl₂, CH₂Br₂) used as the crystalline solvent. X-ray diffraction studies using single crystals clarified the structural distortion of 1 from the regular tetrahedron in pristine 1·15.88H₂O. We revealed that central ammonium stabilizes the distorted structure by forming an intramolecular hydrogen bond with a ligand. By impedance measurements of the crystals, Debye-type dipole relaxations of the guest molecule were observed around 100 K.

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Article information

DOI: https://doi.org/10.1039/D3CE00429E
Article type: Paper
Submitted: 27 Apr 2023
Accepted: 31 Jul 2023
First published: 01 Aug 2023

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CrystEngComm, 2023,25, 4793-4797

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Crystallographic and dielectric studies of tetrahedral {NH₄@Fe₄} crystallized with halomethane molecules

D. Matsumoto, C. Tanaka, M. Fujibayashi, S. Nishihara, K. Takahashi, T. Nakamura, T. Akutagawa, A. Masuya-Suzuki and R. Tsunashima, CrystEngComm, 2023, 25, 4793 DOI: 10.1039/D3CE00429E

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