A6Sb4F12(SO4)3 (A = Rb, Cs): Two Novel Antimony Fluoride Sulfates with Unique Crown-like Clusters
Two new antimony fluoride sulfates named A6Sb4F12(SO4)3 (A = Rb, Cs) with unique crown-like clusters have been successfully synthesized by introducing Sb3+ with a stereochemically active lone pair in the sulfate system through a facile hydrothermal method. The structure regulation induced by the cation sizes results in the symmetry difference in these two title compounds, i.e., Rb6Sb4F12(SO4)3 crystallizing in the polar noncentrosymmetric (NCS) space group of P3 and Cs6Sb4F12(SO4)3 in the centrosymmetric (CS) space group of P1̅. Detailed characterizations, including XRD, thermal behaviors, optical properties, and the theoretical calculations, for these two compounds have been performed. The discovery of the unique crown-like clusters observed in A6Sb4F12(SO4)3 (A = Rb, Cs) enriches the diversity of structures for antimony sulfates systems. Simultaneously, a summary and comparison for all reported antimony halide sulfates has been made to illustrate the synergistic effect of the stoichiometric ratio and cation sizes on the macroscopic centricity and the framework structure, which will guide the systematical discovery of antimony(III)-based functional materials in future.
危险品化学品经营许可证（带存储）