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A novel antimony(III)-based phosphite, SbHPO 3 F, featuring a unique two-dimensional (2D) van der Waals layered structure, has been successfully designed and synthesized via the simultaneous employment of optically active moieties including SbO 3 F seesaw and tetrahedral HPO 3 groups. Its optimized layered arrangement formed by the alternating connection of 4-membered rings (4-MRs) and 8-MRs endows the title compound with desirable optical properties including a large birefringence and short ultraviolet (UV) cutoff edge, implying that it is a potential UV birefringent material.

A novel alkali metal lead halide nitrate, Cs 2 Pb(NO 3 ) 2 Br 2 , has been successfully synthesized via a hydrothermal method. Interestingly, the title compound features a distinctive Ruddlesden-Popper perovskite-like layered structure, which induces the outstanding multifunctional optical properties, including a large birefringence (0.147@546 nm) and broad light-orange emission. Detailed structural analysis and theoretical calculations revealed that the large birefringence originates from the p-π interaction between the Pb 2+ cations and NO 3 groups and that the excellent luminescence properties derive from the distortion of PbO 4 Br 4 polyhedra. This work not only enriches the variant structure types of layered perovskites but also guides the further exploration of all-inorganic multifunctional optical materials.

Developing effective strategies to design novel, excellent birefringent materials has become an emerging challenge. Herein, we report a new UV nitrate birefringent material, CsHgNO 3 Cl 2 , which is an analogue of the known UV carbonate nonlinear optical crystal KCaCO 3 F. In CsHgNO 3 Cl 2 , a perfect layered structure was produced owing to the alliance of a planar π-conjugated anion NO 3 - and highly electropolarized Hg 2+ cation. The optimized layered structure that is beneficial in enlarging the optical anisotropy induced a large birefringence (Δ n = 0.145@546 nm) for CsHgNO 3 Cl 2 , even superior to that of the well-known commercial birefringent material α-BBO in the UV region. The strategy that the optimization of planar functional group arrangement is able to boost birefringence is expected to guide the development of high-performance birefringent materials in the future, especially in the field of UV.

Two new antimony fluoride sulfates named A 6 Sb 4 F 12 (SO 4 ) 3 (A = Rb, Cs) with unique crown-like clusters have been successfully synthesized by introducing Sb 3+ 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., Rb 6 Sb 4 F 12 (SO 4 ) 3 crystallizing in the polar noncentrosymmetric (NCS) space group of P 3 and Cs 6 Sb 4 F 12 (SO 4 ) 3 in the centrosymmetric (CS) space group of P 1̅. 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 A 6 Sb 4 F 12 (SO 4 ) 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.