Anomalous dielectric behaviour in centrosymmetric organic–inorganic hybrid chlorobismuthate(III) containing functional N,N-dimethylethylammonium ligand. Crystal structure and properties

The structure of [C2H5NH(CH3)2+]3[BiCl6−] (abbreviated as DCB) was determined by a single-crystal X-ray diffraction at 115 K. The compound adopts tetragonal symmetry with the space group I41/acd; a = 23.35 Å, c = 17.60 Å, V = 9598 Å3 and Z = 16. The crystal structure of DCB is built up of isolated [BiCl6]3− units and N,N-dimethylethylammonium counterions that are accommodated in the large voids. At ambient temperature two-thirds of the counterions appear to be dynamically disordered. Dynamics of this type of cations contributes to the enhanced dielectric permittivity of DCB. A low frequency dielectric relaxation process that takes place between 200 and 300 K is characterized by an exceptionally large dielectric increment, Δϵ > 100, which is unprecedented in nonferroelectric materials. The molecular motions of the N,N  -dimethylethylammonium cations were studied by means of H1 NMR spin-lattice relaxation time measurements.

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► Novel organic–inorganic hybrid chlorobismuthate(III).
► Unprecedented dielectric response in non-polar material.
► Dielectric relaxation characterized by an exceptionally large dielectric increment.
► The NMR measurements confirmed dynamic disorder of cations.