Abstract
A novel organic ionic plastic crystal (OIPC) based on a quaternary ammonium cation and a tetrachloroferrate anion has been synthesized with the intention of combining the properties of the ionic plastic crystal and the magnetism originating from the iron incorporated in the anion. The thermal analysis of the obtained OIPC showed a solid-solid phase transition below room temperature and a high melting point above 220 °C, indicating their plastic crystalline behaviour over a wide temperature range, as well as thermal stability up to approximately 200 °C. The magnetization measurements show the presence of three-dimensional antiferromagnetic ordering below 4 K. The results from electrochemical characterization display a solid-state ionic conduction sufficiently high and stable (between 10(-2.7) and 10(-3.6) S cm(-1) from 20 to 180 °C) for electrochemical applications.
Highlights
Plastic crystal substances were described in the 1960s by Timmermans[18] on molecular based compounds
The transition metalcontaining plastic phase could be part of these auspicious new materials where the introduction of structural functionalities into the anionic part makes it possible to design new plastic crystal phases with targeted properties. It will favourably combine the properties of the ionic plastic crystal with the magnetism, originating from the metal incorporated in the anion
While other plastic crystals based on the quaternary ammonium ions, like choline[39] or tetramethylammonium,[40] present several solid– solid transitions detected using differential scanning calorimetry (DSC) analysis,[4] choline[FeCl4] shows only one solid–solid (s–s) phase transition at around 260 K upon cooling from the room temperature [Fig. 1(a)]
Summary
Plastic crystal substances were described in the 1960s by Timmermans[18] on molecular based compounds. Metal–organic frameworks for which chemical or physical properties can be tuned by applying an external stimulus are attracting significant interest in view of their potential applications as chemical switches or molecular sensors.[22] The transition metalcontaining plastic phase could be part of these auspicious new materials where the introduction of structural functionalities into the anionic part makes it possible to design new plastic crystal phases with targeted properties. It will favourably combine the properties of the ionic plastic crystal with the magnetism, originating from the metal incorporated in the anion. We display the electrochemical performance, as well as the magnetic properties using dc and ac magnetic measurements and Mossbauer spectroscopy
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