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Molecular motion of halogenated ethylammonium/[18]crown-6 supramolecular ions in nickel dithiolate magnetic crystals

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Title: Molecular motion of halogenated ethylammonium/[18]crown-6 supramolecular ions in nickel dithiolate magnetic crystals
Authors: Hasuo, Naohiro Browse this author
Takahashi, Kiyonori Browse this author →KAKEN DB
Hisaki, Ichiro Browse this author →KAKEN DB
Kokado, Kenta Browse this author →KAKEN DB
Nakamura, Takayoshi Browse this author →KAKEN DB
Issue Date: 14-Apr-2021
Publisher: Royal Society of Chemistry
Journal Title: CrystEngComm
Volume: 14
Start Page: 2756
End Page: 2763
Publisher DOI: 10.1039/d1ce00253h
Abstract: Supramolecular cations, consisting of ethylammonium derivatives (X-CH2CH2-NH3+) complexed with [18] crown-6, were incorporated into [Ni(dmit)(2)](-) crystals in order to promote molecular motion. Crystals of (X-CH2CH2-NH3+)([18]crown-6)[Ni(dmit)(2)](-) (1: X = H, 2: X = F, 3: X = Cl and 4: X = Br) were prepared for this purpose. Although large amplitude molecular motions do not occur in crystal 1, dynamic disorder of F-CH2 groups takes place between two sites in crystal 2. Similar disorder of Cl-CH2 groups along with rotation of [18]crown-6 molecules also exists in crystal 3. Crystal 4 exhibits dynamic disorder of Br-CH2-CH2 groups between four sites. This is especially the case for crystal 4 which undergoes a distinct dielectric response with relaxer-like behavior in the temperature dependence of the dielectric loss tangent. Interactions between [Ni(dmit)(2)](-) ions in all crystals are antiferromagnetic, and the magnitudes of the interactions are qualitatively consistent with the strength of intermolecular interactions estimated from transfer integrals, where interactions within [Ni(dmit)(2)](-) dimers are the larger than the others in all crystals.
Type: article (author version)
Appears in Collections:電子科学研究所 (Research Institute for Electronic Science) > 雑誌発表論文等 (Peer-reviewed Journal Articles, etc)

Submitter: 高橋 仁徳

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