Journal
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
Volume 116, Issue 13, Pages 5878-5885Publisher
NATL ACAD SCIENCES
DOI: 10.1073/pnas.1817866116
Keywords
ferroelectricity; homochirality; enantiomer; ferroelectric domains
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Funding
- Nanchang University
- National Natural Science Foundation of China [21831004, 21427801, 91422301, 91856114]
- Young Elite Scientists Sponsorship Program by China Association for Science and Technology [2018QNRC001]
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For nearly 100 y, homochiral ferroelectrics were basically multicomponent simple organic amine salts and metal coordination compounds. Single-component homochiral organic ferroelectric crystals with high-Curie temperature (T-c) phase transition were very rarely reported, although the first ferroelectric Rochelle salt discovered in 1920 is a homochiral metal coordination compound. Here, we report a pair of single-component organic enantiomorphic ferroelectrics, (R)-3-quinuclidinol and (S)-3-quinuclidinol, as well as the racemic mixture (Rac)-3-quinuclidinol. The homochiral (R)- and (S)-3-quinuclidinol crystallize in the enantiomorphic-polar point group 6 (C-6) at room temperature, showing mirror-image relationships in vibrational circular dichroism spectra and crystal structure. Both enantiomers exhibit 622F6-type ferroelectric phase transition with as high as 400 K [above that of BaTiO3 (T-c = 381 K)], showing very similar ferroelectricity and related properties, including sharp step-like dielectric anomaly from 5 to 17, high saturation polarization (7 mu C/cm(2)), low coercive field (15 kV/cm), and identical ferroelectric domains. Their racemic mixture (Rac)-3-quinuclidinol, however, adopts a centrosymmetric point group 2/m (C-2h), undergoing a nonferroelectric high-temperature phase transition. This finding reveals the enormous benefits of homochirality in designing high-T-c ferroelectrics, and sheds light on exploring homochiral ferroelectrics with great application.
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