A new class of ferroelectric coordination-based polymers has been developed by the self-assembly of lipophilic zinc porphyrin (ZnP) and ditopic bridging ligands. The ligands contain dipolar benzothiadiazole or fluorobenzene units, which are axially coordinated to ZnP with the dipole moments oriented perpendicular to the coordination axes. The coordination-based polymers show ferroelectric characteristics in the liquid crystalline state, as revealed by distinctive hysteresis in the polarization-electric field (P-E) loops and inversion current peaks in current-voltage (I-V) loops. The observed ferroelectric properties are explainable by flip-flop rotation of the dipolar axle ligands induced by the applied electric field, as demonstrated by the positive-up-negative-down (PUND) measurements. The present system provides a new operating principle in supramolecular ferroelectrics.

A new class of supramolecular ferroelectrics has been developed by the self‐assembly of mesogenic zinc porphyrin and bridging ligands carrying large dipoles. These complexes show distinctive hysteresis in the polarization–electric field (P–E) loops in the liquid crystalline state as a result of electric field‐induced flip–flop rotation of the dipolar axial ligands around the coordination axis. It gives a new operating principle for supramolecular ferroelectrics. More information can be found in the Full Paper by N. Kimizuka et al. on page 14213 ff.