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A novel open-framework cadmium selenite bromide, [Cd10(SeO3)8Br4]·HBr·H2O (1), has been obtained by a solid-state reaction at 450°C, and the structure has been determined by single-crystal X-ray diffraction analysis. Compound 1 crystallizes in Pbcm of the orthorhombic system: a=10.882(3), b=16.275(5), c=18.728(6)Å, V=3317(2)Å3, R1/wR2=0.0411/0.0659. Compound 1 is characteristic of a novel 3-D open-framework structure, composing ∞ 2[CdSeO3] layers and the pillars of edge-shared CdO3Br2 square pyramids. The lattice water molecules and the HBr molecules locate in the voids of the framework. Optical absorption spectrum of 1 reveals the presence of an optical gap of 1.65eV. Solid-state photoluminescent study indicates that compound 1 exhibits strong violet emission. TG–DSC measurement shows that compound 1 is thermally stable up to 200°C. [ABSTRACT FROM AUTHOR]

Mid-far infrared (IR) non-linear optical (NLO) materials are of great importance in military and civil fields. However, commercial IR-NLO crystals (such as AgGaS 2 , AgGaSe 2 and ZnGeP 2 ) do not currently satisfy the requirements of large second-harmonic generation (SHG) and high laser induced damage thresholds (LIDTs), which seriously limits their practical applications. Herein, we have developed a new series of salt-inclusion chalcogenides, [A 3 X][Ga 3 PS 8 ] (A = K, Rb; X = Cl, Br), which are constructed from alternate stacking of adamantane-like [Ga 3 PS 10 ] 6- cluster layers and cationic [A 3 X] 2+ salt layers. Importantly, they display both large SHG responses of several-fold and high LIDTs for dozens of times that of commercial AgGaS 2 , which exhibit the highest LIDTs among the reported IR-NLO materials with a larger SHG conversion efficiency than that of AgGaS 2 . These properties together with wide transparent region, type I phase-matching features and congruent-melting behaviors indicate they are promising IR-NLO materials.