Designing and tuning properties of a three-dimensional porous quaternary chalcogenide built on a bimetallic tetrahedral cluster [M4Sn3S13]5− (M=Zn/Sn)

A multifunctional three-dimensional quaternary chalcogenide [Na5Zn3.5Sn3.5S13]·6H2O has been synthesized by solvothermal reactions. [Na5Zn3.5Sn3.5S13]·6H2O represents an interesting example of metal chalcogenides that combines semiconductivity, porosity, and light emission in a single structure. It crystallizes in the cubic space group Fm-3c, a=17.8630(3) Å, V=5699.85(17) Å3, Z=8. The compound decomposes at ∼450 °C. A band gap of 2.9 eV is estimated from the optical diffuse reflectance data. A strong photoluminescence peak is observed at 2.43 eV in Mn doped samples. The electronic and optical properties of this compound can be systematically tuned by substitution of metal and chalcogen elements.