Observation of Ferrochiral Transition Induced by an Antiferroaxial Ordering of Antipolar Structural Units in Ba(TiO)Cu4(PO4)4

J Am Chem Soc. 2021 Mar 10;143(9):3638-3646. doi: 10.1021/jacs.1c00391. Epub 2021 Feb 25.

Abstract

Ferrochiral transition, i.e., a transition involving an emergence of chirality, provides an unique opportunity to achieve a nonvolatile reversible control of chirality with external fields. However, materials showing pure ferrochiral transitions, which are accompanied by no other types of ferroic transition, are exceedingly rare. In this study, we propose that a pure ferrochiral transition is achieved by a combination of antipolar and antiferroaxial orderings of structural units, and substantiate this proposal through a study of the chiral compound Ba(TiO)Cu4(PO4)4. Single crystal X-ray diffraction measurements have revealed that this material undergoes a second order ferrochiral transition whose order parameter is described by an antiferroaxial (staggered) rotation of antipolar structural units, thus demonstrating our proposal. Furthermore, by measuring spatial distributions of optical rotation, we successfully visualized a temperature evolution of ferrochiral domains across the transition temperature and demonstrated the relationship between chirality and optical rotation. This work provides a guide to find a pure ferrochiral transition, thus providing an opportunity to achieve a ferroic control of chirality.