Tailoring the physical properties of hybrid magnetic quinuclidine-based plastic compounds via weak interactions

Herein we explore the opportunities arising from combining bicyclic amine cations with halometallate anions to build organic–inorganic hybrid materials. We will use the crystal engineering approach in these materials, focusing on the tuning of the organic cation, which is mainly responsible for obtaining both new plastic states at high temperature and electrical behaviour below the plastic temperature. Precisely, this work explores the influence of the ketonization of the bicyclic quinuclidine molecule (C 7 H 13 N) + , which, combined with the tetrachloroferrate(1-) anion, gives the compound (3-oxoquinuclidinium)[FeCl 4 ]. Interestingly, crystallization in the presence of humidity is enough to obtain an isostructural hydrate phase of formula (3-oxoquinuclidinium)[FeCl 4 ]·H 2 O. Although the organic–inorganic layered structure is the same in both compounds, the three-dimensional magnetic ordering disappears after the intercalation of crystallization water molecules. A heat treatment above 400 K allows the removal of water obtaining the non-hydrate phase. Finally, the temperature evolution of the electric and magnetic behaviour will be compared with other previously reported hybrid organic–inorganic materials built with tetrachloroferrate ions and quinuclidinium-based cations.