Enhanced dielectricity coupled to spin-crossover in a one-dimensional polymer iron(ii) incorporating tetrathiafulvalene†
Abstract
In designing multifunctional materials for potential switches that can be used as memory devices, the high-spin (HS) to low-spin (LS) crossover (SCO) one-dimensional polymer, [FeII(L)(4,4′-bpy)]n, was constructed from a designed redox-active tetrathiafulvalene (TTF) functionalized Schiff-base and the ditopic linker 4,4′-bipyridine (bpy). It exhibits an 8 K hysteretic SCO centred at T1/2 = 325 K which is coupled to changes in its dielectric constant. The crystal structures above and below the transition temperature reveal similar parallel linear ⋯Fe–bpy–Fe–bpy⋯ chains displaying expansion of the FeII octahedron in the HS state. Density functional theory (DFT) calculations reveal a concerted electronic charge and spin change represented by the Mülliken charge of the Fe and the magnitude and direction of the dipole moment which substantiate the experimental observations.
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