[Zn10(µ4-S)(µ3-S)6(Py)9(SO4)3] as a molecular model of ZnS surfaces: an experimental and theoretical study

Experimental and theoretical results pertaining to [Zn10(µ4-S)(µ3-S)6(Py)9(SO4)3], a possible molecular model of ZnS S-terminated polar surfaces, as well as a potential source of strictlymonodispersed ZnS quantum dots, are presented and discussed. The results of density functional theory (DFT) calculations provided a rationale for the peculiar arrangement of [Zn10(l4-S)(l3-S)6(Py)9(SO4)3] clusters in the solid state, contemporarily indicating the unsuitability of the isolated species to mimic whatever (polar or non-polar) ZnS surface. Despite the fact that such a failure is further confirmed by time-dependent DFT and UV–Vis diffuse reflectance spectroscopy, the combined use of theoretical outcomes, DRIFT measurements, and literature data pertaining to the surface chemical properties of ZnS (Hertl in Langmuir 4:594, 1988) ultimately testifies that [Zn10(µ4-S)(µ3-S)6(Py)9(SO4)3] is perfectly suited to model the interaction of pyridine molecules with ZnS surface Lewis acid sites. The herein reported theoretical results are expected to be a useful reference for the interpretation of chemisorption experiments of Py-based Lewis bases on single crystal ZnS surfaces.