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High‐Temperature and Large‐Polarization Ferroelectric with Second Harmonic Generation Response in a Novel Crown Ether Clathrate
Author(s) -
Han Ding Chong,
Tan Yu Hui,
Li Yu Kong,
Wen Jia Hui,
Tang Yun Zhi,
Wei Wen Juan,
Du Peng Kang,
Zhang Hao
Publication year - 2021
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202101707
Subject(s) - ferroelectricity , dielectric , second harmonic generation , phase transition , materials science , differential scanning calorimetry , hysteresis , polarization (electrochemistry) , condensed matter physics , clathrate hydrate , crystallography , optoelectronics , optics , chemistry , hydrate , organic chemistry , thermodynamics , physics , laser
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: [(C 6 H 5 NF 3 )(18‐crown‐6)][BF 4 ] ( 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 / cm 2 . 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.

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