RESUMEN
A novel type of supertetrahedral connectivity is exhibited by the 72-atom discrete supercubooctahedron in (Cs6Cl)2Cs5[Ga15Ge9Se48] (1), which undergoes both cation and anion exchange, as revealed by unambiguous single-crystal X-ray diffraction data. Electronic-structure studies helped to understand the Ge/Ga distribution.
RESUMEN
A novel noncentrosysmmetric sulfide, Pb5Ga6ZnS15 (1), was synthesized for the first time. Its crystal structure revealed the presence of [GaS2](-)∞ (chain 1, chains of [GaS4](5-) tetrahedra) and [Ga4S9](6-)∞ (chain 2, chains of T2-supertetrahedra) connected by isolated [ZnS4](6-) tetrahedra. Structure correlation with the network constructed solely using chain 1 (Pb4Ga4GeQ12-type) is discussed. Pb5Ga6ZnS15 was calculated to have a suitable static briefringence (Δn) of 0.1137, and a large nonlinear optical susceptibility d31 of 58.32 pm V(-1) at a wavelength of 2.05 µm (0.6 eV), much higher than that of the benchmark AgGaS2 (18.14 pm V(-1)).