AIB3 IIC2 IIIQ6 VIXVII: A Thioborate Halide Family for Developing Wide Bandgap Infrared Nonlinear Materials by Coupling Planar [BS3] and Polycations.

Developing high-performance infrared (IR) nonlinear optical (NLO) materials is urgent but challenging due to the competition between NLO coefficient and bandgap in one compound. Herein, by coupling NLO-active [BS3] planar units and halide-centered polycations, six new metal thioborate halides ABa3B2S6X (A = Rb, Cs; X = Cl, Br, I) composed of zero-dimensional [XBamRbn/Csn] polycations and [BS3] units, belonging to a new A I B 3 II C 2 III Q 6 VI X VII ${\mathrm{A}}^{\mathrm{I}}{\mathrm{B}}_{3}^{\mathrm{II}}{\mathrm{C}}_{2}^{\mathrm{III}}{\mathrm{Q}}_{6}^{\mathrm{VI}}{\mathrm{X}}^{\mathrm{VII}}$ family, are rationally designed and fabricated. The compounds show an interesting structural transition from Pbcn (ABa3B2S6Cl) to Cmc21 (ABa3B2S6Br and ABa3B2S6I) driven by the clamping effect of polycationic frameworks. ABa3B2S6Br and ABa3B2S6I are the first series metal thioborate halide IR NLO materials, and the introduction of [BS3] unit effectively widens the bandgap of planar unit-constructed chalcogenides. ABa3B2S6Br and ABa3B2S6I, exhibiting wide bandgaps (3.55-3.60 eV), high laser-induced damage thresholds (≈ 6 × AgGaS2), and strong SHG effects (0.5-0.6 × AgGaS2) with phase-matching behaviors, are the promising IR NLO candidates for high-power laser applications. The results enrich the chemical and structural diversity of boron chemistry and give some insights into the design of new IR NLO materials with planar units.

Synthesis, structures and properties of two new selenite optical materials: K2Zn3Se4O12 and K4Zn3V4Se2O19.

Two new selenites, K2Zn3Se4O12 (compound 1) and K4Zn3V4Se2O19 (compound 2), have been successfully synthesized by solid-state reactions in vacuum tubes. Compound 1 consists of a three-dimensional (3D) framework with [SeO3] triangular pyramids and [ZnO4] tetrahedra in the monoclinic space group P21/c (No. 14). Compound 1's cut-off edge is below 344 nm, based on its UV-Vis-NIR diffuse reflectance studies, and theoretical calculations indicate a birefringence of around 0.043 at 1064 nm. The two-dimensional layer of compound 2, in contrast, is made up of [SeO3] triangular pyramids, [ZnO4] tetrahedra, and [V4O13] tetrahedra. It crystallizes in the monoclinic space group C2/c (No. 15). Its UV-Vis-NIR diffuse reflectance studies demonstrate that the compound's cut-off edge is lower than 330 nm.