摘要：Borates are among a class of compounds that exhibit rich structural diversity and find wide applications. The formation of edge-sharing ( es -) BO4 tetrahedra is extremely unfavored according to Pauling’s third and fourth rules. However, as the first and the only es- borate obtained under ambient pressure, es -KZnB3O6 shows an unexpected high thermal stability up to its melting point. The origin of this extraordinary stability is still unclear. Here, we report a novel property in KZnB3O6: unidirectional thermal expansion, which plays a role in preserving es- BO4 from disassociation at elevated temperatures. It is found that this unusual thermal behavior originates from cooperative rotations of rigid groups B6O12 and Zn2O6, driven by anharmonic thermal vibrations of K atoms. Furthermore, a detailed calculation of phonon dispersion in association with this unidirectional expansion predicts the melting initiates with the breakage of the link between BO3 and es- BO4. These findings will broaden our knowledge of the relationship between structure and property and may find applications in future.
