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Borates are among a class of compounds that exhibit rich structural diversity and find wide applications. The formation of edge-sharing ( es -) BO 4  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 -KZnB 3 O 6  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 KZnB 3 O 6 : unidirectional thermal expansion, which plays a role in preserving  es- BO 4  from disassociation at elevated temperatures. It is found that this unusual thermal behavior originates from cooperative rotations of rigid groups B 6 O 12  and Zn 2 O 6 , 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 BO 3  and  es- BO 4 . These findings will broaden our knowledge of the relationship between structure and property and may find applications in future.

Unidirectional thermal expansion in edge-sharing BO4 tetrahedra contained KZnB3O6