A Noncentrosymmetric Metal-Free Borophosphate: Achieving a Large Birefringence and Excellent Stability by Covalent-Linkage.

Organic-inorganic hybrid linear and nonlinear optical (NLO) materials have received increasingly wide spread attention in recent years. Herein, the first hybrid noncentrosymmetric (NCS) borophosphate, (C5H6N)2B2O(HPO4)2 (4PBP), is rationally designed and synthesized by a covalent-linkage strategy. 4-pyridyl-boronic acid (4 PB) is considered as a bifunctional unit, which may effectively improve the optical properties and stability of the resultant material. On the one hand, 4 PB units are covalently linked with PO3(OH) groups via strong B-O-P connections, which significantly enhances the thermal stability of 4PBP (decomposition at 321, vs lower 200 °C of most of hybrid materials). On the other hand, the planar π-conjugated C5H6N units and their uniform layered arrangements represent large structural anisotropy and hyperpolarizability, achieving the largest birefringence (0.156 @ 546 nm) in the reported borophosphates and a second-harmonic generation response (0.7 × KDP). 4PBP also exhibits a wide transparency range (0.27-1.50 µm). This work not only provides a promising birefringent material, but also offers a practical covalent-attachment strategy for the rational design of new high-performance optical materials.

Optically Anisotropic Mixed-Metal Fluoroiodate Ba2[GaF5(IO3F)] with a Wide Optical Transparent Window and a Moderate Birefringence.

An optically anisotropic alkali-earth-metal gallium fluoroiodate, Ba2[GaF5(IO3F)] (1), was ingeniously obtained by integrating fluoride and fluoroiodate functional units under moderate hydrothermal conditions. It features a three-dimensional (3D) structure constructed by the highly polarizable fluoroiodate unit [IO3F] and the fluoride groups [GaOF5] and [BaO3Fx] (x = 6, 7). The compound is stable at temperatures up to 500 °C. With the synergistic interaction between [IO3F] and the fluoride groups, the mixed-metal fluoroiodate induces a short ultraviolet cutoff edge at about 230 nm, a medium measured birefringence of 0.068 @ 550 nm, and a wide optical transparent window (0.34-11.9 µm), indicating that 1 has potential applications as a birefringent material from near-UV to mid-infrared. Theoretical calculations prove that the optical characteristics of the compound are mainly attributed to [IO3F] and the fluoride functional groups. This work demonstrates that the presence of various specific functional groups in compounds will help to develop promising inorganic functional materials possessing good optical performance.

YSO4F·H2O: A Deep-Ultraviolet Birefringent Rare-Earth Sulfate Fluoride with Enhanced Birefringence Induced by Fluorinated Y-Centered Polyhedra.

Birefringent crystals can modulate and detect the polarization of light and are important optical functional materials. The birefringence is positively correlated to the anisotropy of the structure. By partially substituting sulfate anion with large electronegative fluorine in the parent compound Y2(SO4)3·8H2O, a new fluorinated rare-earth sulfate YSO4F·H2O with enhanced anisotropy was achieved. YSO4F·H2O features a dense 3D structure constructed by the polarizable [YOF] polyhedra and [SO4] tetrahedra. The diffuse reflectance spectrum reveals that it has a short UV absorption edge of below 200 nm. The substitution of the F- ion enhances the optical anisotropy, making the material exhibit an enhanced birefringence (0.0357 at 546 nm), which is 5.1 times that of the parent compound and is also larger than most deep-UV birefringent sulfates. It is expected that this work may shed useful insights in the exploration of deep-UV birefringent materials with enhanced optical performances..