High-Temperature and Large-Polarization Ferroelectric with Second Harmonic Generation Response in a Novel Crown Ether...

Molecular ferroelectrics of high-temperature reversible phase transitions are very rare and have attracted increasing attention in recent years. In this paper is described the successful synthesis of a novel high-temperature host-guest inclusion ferroelectric: [(C₆ H₅ NF₃ )(18-crown-6)][BF₄ ] (1) that shows a pair of reversible peaks at 348 K (heating) and 331 K (cooling) with a heat hysteresis about 17 K by differential scanning calorimetry measurements, thus indicating that 1 undergoes a reversible structural phase transition. Variable-temperature PXRD and temperature-dependent dielectric measurements further prove the phase-transition behavior of 1. The second harmonic response demonstrates that 1 belongs to a non-centrosymmetric space group at room temperature and is a good nonlinear optical material. In its semiconducting properties, 1 shows a wide optical band gap of about 4.43 eV that comes chiefly from the C, H and O atoms of the crystals. In particular, the ferroelectric measurements of 1 exhibit a typical polarization-electric hysteresis loop with a large spontaneous polarization (P_s ) of about 4.06 μC/cm² . This finding offers an alternative pathway for designing new ferroelectric-dielectric and nonlinear optical materials and related physical properties in organic-inorganic and other hybrid crystals.