2024-03-28T12:19:52Zhttps://eprints.lib.hokudai.ac.jp/dspace-oai/requestoai:eprints.lib.hokudai.ac.jp:2115/848502022-11-17T02:08:08Zhdl_2115_20057hdl_2115_148Molecular motion of halogenated ethylammonium/[18]crown-6 supramolecular ions in nickel dithiolate magnetic crystalsHasuo, Naohiro1000090812595Takahashi, Kiyonori1000090419466Hisaki, Ichiro1000040600226Kokado, Kenta1000060270790Nakamura, Takayoshiopen access430Supramolecular 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.Royal Society of Chemistry2021-04-14engjournal articleAMhttp://hdl.handle.net/2115/84850https://doi.org/10.1039/d1ce00253h1466-8033CrystEngComm1427562763https://eprints.lib.hokudai.ac.jp/dspace/bitstream/2115/84850/1/Man%20%20XEtAm_18C6_CrystEngComm_HUSCUP.pdfapplication/pdf1.89 MB2021-04-14https://eprints.lib.hokudai.ac.jp/dspace/bitstream/2115/84850/2/XEtAm_18C6_SI_revised2.docxapplication/vnd.openxmlformats-officedocument.wordprocessingml.document2.61 MB2021-04-14