Dielectric Relaxation and Beyond Limiting Behavior of Alternating-Current Conductivity in a Supermolecular Ferroelectric.

A cyclen-based hybrid supermolecule crystal, [(FeCl2 )(cyclen)]Cl (1), where cyclen=1,4,7,10-tetraazacyclododecane, was prepared using a liquid-liquid diffusion approach. The variable crystal structures exhibit that compound 1 belongs to an orthorhombic crystal system, Pna21 space group (point group C2V ) in the temperature range of 150-400 K. This hybrid supermolecule shows a dielectric relaxation behavior around room temperature, and the ferroelectric nature of 1 has been directly verified by hysteresis measurements. In addition, the AC (alternating current) conductivity study reveals that the 1 displays a beyond limiting behavior. These interesting findings are for the first time reported in the field of supermolecular ferroelectrics. This study may open a new way to construct supermolecular ferroelectrics and give insights into their conductor behavior.

[(18-Crown-6)K][Fe(1)Cl(1)4 ]0.5 [Fe(2)Cl(2)4 ]0.5 : A Multifunctional Molecular Switch of Dielectric, Conductivity and Magnetic Properties.

Multifunctional materials that exhibit different physical properties in a single phase have potential for use in multifunctional devices. Herein, we reported an organic-inorganic hybrid compound [(18-crown-6)K][Fe(1)Cl(1)4 ]0.5 [Fe(2)Cl(2)4 ]0.5 (1) by incorporating KCl and FeCl3 into a 18-crown-6 molecule, which acts as a host of the six O atoms providing a lone pair of electrons to anchor the guest potassium cation, and [FeCl4 ]- as a counterion for charge balance to construct a complex salt. This salt exhibited a one-step reversible structural transformation giving two separate high and low temperature phases at 373 K, which was confirmed by systematic characterizations including differential scanning calorimetry (DSC) measurements, variable-temperature structural analyses, and dielectric, impedance, variable-temperature magnetic susceptibility measurements. Interestingly, the structural transformation was coupled to both hysteretic dielectric phase transition, conductivity switch and magnetic-phase transition at 373 K. This result gives an idea for designing a new type of phase-transition materials harboring technologically important magnetic, conductivity and dielectric properties.