Stereoactive oxysalts can exhibit excellent nonlinear optical coefficients and linear optical properties, like large birefringence and strong second harmonic generation (SHG) intensity, due to the stereo-chemically active lone pair electrons. Recently, a series of stereoactive oxysalts with new structures and strong performances have been reported, such as RbTeMo2O8F (27 × KDP, 0.263@546 nm), Pb2Bi(SeO3)2Cl3 (13.5 × KDP, 0.186@1064 nm), Y3F(SeO3)4 (5.5 × KDP, 5.03 eV), Bi(IO3)F2 (11.5 × KDP, 0.209@1064 nm) and K2Sb(P2O7)F (4.0 × KDP, 0.157@546 nm), etc. In this review, we summarized the recent progresses on stereoactive oxysalts by focusing on their structures and linear/nonlinear optical applications, surveying over a thousand newly reported compounds. Based on the different types of the centered cations, the reported stereoactive oxysalts compounds were classified into five different categories, metal antimonites, metal selenites, metal tellurites, metal iodates and metal bromates. We believe that stereoactive oxysalts are the promising candidates for many advanced functional materials and hope this paper can provide some perspectives for the development of new stereoactive oxysalts. More importantly, this comprehensive review not only introduces the rich structural and chemical properties of stereoactive oxysalts for graduate students and postdoctoral researchers, but also serves as a comprehensive reference for researchers studying optical properties of stereoactive oxysalts materials. 

A survey of stereoactive oxysalts for linear and nonlinear optical applications

The new zirconium fluoride, K3Ba2Zr6F31, is reported, featuring unprecedented acentric cis-[Zr6F34]10− clusters composed of ZrF8 units, which display a moderate second-harmonic generation response (0.5 × KH2PO4) and short UV cutoff edge (below 200 nm).

Exploring a new short-wavelength nonlinear optical fluoride material featuring unprecedented polar cis-[Zr6F34]10− clusters

CsSn2(HPO3)2I: The first inorganic metal phosphite iodide as a promising birefringent material exhibits a large birefringence with ideally layered framework

Old tree blossoms anew: Research progress on the structures and optical properties of ultraviolet selenites

Macroscopic polarization enhancement boosting piezo-photocatalytic performance via Nb-doping on B-site of Bi
 4Ti
 3O
 12 nanosheets

Perovskite structure compounds are significant candidates for designing new optical function materials due to their structural variability. Here, an inorganic tetravalent cerium fluoride, Na2 CeF6 , is derived from the perovskite structure through double-site cation co-substitution. Na2 CeF6 crystalizes in the non-centrosymmetric space group P 6 ¯ 2 m ${P}^{\bar{6}}2m$ . Edge-sharing connected NaF9 and CeF9 polyhedra build the whole 3D structure of Na2 CeF6 . Importantly, it represents the first Ce(IV) fluoride nonlinear optical (NLO) crystal and can produce a strong and phase-matchable second-harmonic generation (SHG) effect of ≈2.1 times that of KH2 PO4 (KDP), making it the strongest among non-lone pair electron metal fluoride system. Further, it exhibits a high laser-induced damage threshold (LIDT) of 74.65-76.25 MW cm-2 , which is over 20 times that of AgGaS2 . It also exhibits a wide transparent region (0.5-14.3 µm). This work provides a facile route for exploring high-performance halide NLO materials.

Na2 CeF6 : A Highly Laser Damage-Tolerant Double Perovskite Type Ce(IV) Fluoride Exhibiting Strong Second-Harmonic Generation Effect.

Combining multiple anions to design compounds with novel structures and excellent optical properties has become a hot research field. In this paper, a novel nitrate oxyfluoride, Hg3O2(NO3)F, has been obtained....

Hg3O2(NO3)F: A mercury nitrate oxyfluoride with unprecedented [(Hg3O2F)+]∞ cationic framework and excellent optical anisotropy

Compounds constructed by mixed anions are widely favorable for their diverse crystal structures and physical performances. Here, two lead phosphite halides, Pb2Cl2(HPO3)(H2O) (1) and Pb3Br2(HPO3)2 (2), were obtained by facile hydrothermal reactions. Both compounds crystallize in the space group Pnma. 1 exhibits a 3D structure composed of HPO3 units, PbCl4O3 pentagonal bipyramids, and PbO3 pyramids. 2 also shows a 3D framework built by HPO3 units, PbO2Br4 octahedron, PbO5 and PbO3Br2 square pyramids. By introducing halogen anions to the lead phosphite system, 1 and 2 show enhanced birefringences of 0.083 and 0.072 at 1064 nm, respectively, compared with 0.023@1064 nm for Pb2(HPO3)2. In this work, syntheses, crystal structures, optical properties, and theoretical calculation results have been studied in detail.

https://pubs.acs.org/doi/pdf/10.1021/acs.inorgchem.2c04331

Pb2Cl2(HPO3)(H2O) and Pb3Br2(HPO3)2: Two Phosphite Halides with 3D Structural Networks and Enlarged Birefringence.

Designing new compounds based on anion regulation has been widely favored due to the production of diverse crystal structures and excellent optical properties. Here, a new nitrate oxyfluoride, Hg16O12(NO3)6F2(H2O), has been obtained through a hydrothermal reaction. It crystallizes in the centric Ibca space group and shows a novel three-dimensional [(Hg16O12F2(H2O))6+]∞ cationic framework composed of interconnected HgO2F, HgO3, and HgO2(H2O) units, with isolated NO3– groups as balanced anions to build the whole structure. Notably, the HgO2F and HgO2(H2O) units are first presented here among mercury (Hg)-based compounds. Additionally, Hg16O12(NO3)6F2(H2O) exhibits a large birefringence of 0.17 at 546 nm. This work enriches the multiformity of Hg-based compounds and provides a route for developing promising birefringent materials. 

Hg16O12(NO3)6F2(H2O): A Mercury-Rich Nitrate Oxyfluoride with Diverse Triple-Coordinated Mercury-Based Units That Exhibits an Unparalleled [(Hg16O12F2(H2O))6+]∞ Cationic Framework and a Large Birefringence.

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