Organic enantiomeric high- T c ferroelectrics

对映体 材料科学 立体化学 化学
作者
Peng‐Fei Li,Wei‐Qiang Liao,Yuan‐Yuan Tang,Wen‐Cheng Qiao,Dewei Zhao,Yong Ai,Ye‐Feng Yao,Ren‐Gen Xiong
出处
期刊:Proceedings of the National Academy of Sciences of the United States of America [National Academy of Sciences]
卷期号:116 (13): 5878-5885 被引量:184
标识
DOI:10.1073/pnas.1817866116
摘要

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 (Tc) 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 (C6) 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 (Tc = 381 K)], showing very similar ferroelectricity and related properties, including sharp step-like dielectric anomaly from 5 to 17, high saturation polarization (7 μC/cm2), low coercive field (15 kV/cm), and identical ferroelectric domains. Their racemic mixture (Rac)-3-quinuclidinol, however, adopts a centrosymmetric point group 2/m (C2h), undergoing a nonferroelectric high-temperature phase transition. This finding reveals the enormous benefits of homochirality in designing high-Tc ferroelectrics, and sheds light on exploring homochiral ferroelectrics with great application.
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