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Amantadine-based coordination systems with Co(II) and Zn(II) chlorides
A Ciżman1, D A Kowalska2, M Gusowski1
1Department of Experimental Physics, Wrocław University of Science and Technology, Wybrzeże Wyspiańskiego 27, 50-370 Wrocław, Poland. agnieszka.cizman@pwr.edu.pl.
None:
Hybrid organic-inorganic materials based on amantadine (1-adamantylammonium) and tetrahedral metal chloride anions were synthesized and structurally characterized for Co(II) and Zn(II) analogues. The compounds, formulated as (C10H18N)2MeCl4 (Me = Co, Zn), crystallize in the monoclinic C2/m phase at room temperature (RT) and undergo reversible phase transitions to a triclinic structure upon cooling, as confirmed by XRD and DSC measurements. The transitions occur at approximately 272 K (Co) and 260 K (Zn) and are accompanied by pronounced thermal hysteresis and entropy changes consistent with an order-disorder mechanism. The structural transformation is governed by the reorganization of the amantadine cations and a cooperative rearrangement of the N-H⋯Cl hydrogen-bonding network linking the organic and inorganic sublattices. Dielectric spectroscopy reveals clear anomalies in the permittivity near the transition temperatures, while Cole-Cole analysis indicates a well-defined thermally activated relaxation process in the Co compound, whereas this process is absent or strongly suppressed in the Zn analogue. DC conductivity follows Arrhenius behavior in both compounds, with changes in activation energy across the transition reflecting modified proton-transfer pathways. These results demonstrate that the nature of the metal center tunes hydrogen-bond dynamics, dipolar relaxation, and charge transport, highlighting amantadine-based halometalates as promising candidates for switchable dielectric and proton-conducting hybrid materials.
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