An experimental and theoretical study of the electronic and molecular structure of [Zn4(?4-S){μ-S_2P(OC_2H_5)_2}_6]: the first molecular model of ZnS

摘要

The electronic and molecular structure of hexakis[μ-(O,O′-diethyl dithiophosphate-S:S′)]-μ_4-thiotetrazinc, [Zn_4(μ_4-S){μ-S_2P(OC_2H_5)_2}_6] (1), has been investigated by combining X-ray diffraction measurements, UV-vis absorption spectroscopy and density functional calculations. The title compound is characterized by a Zn_4(μ_4-S)(μ-S_(12)) core consisting of a S atom at the center of a distorted tetrahedron of Zn ions, each of them placed at the center of an irregular tetrahedron of S atoms. Theoretical results point out that 1, at variance to the isostructural [Zn_4(μ_4-S){μ-S_2As(CH_3)_2}_6] recently investigated by Albinati et al. {Inorg. Chem. 38 (1999) 1145], can be considered a well tailored molecular model of ZnS. Theoretical outcomes also indicate that the low energy region of the UV absorption spectrum of 1 includes transitions having a ligand-to-metal-charge transfer nature involving the excitation of an electron from the occupied μ_2-S 3p based atomic orbitals to the empty Zn 4s based levels.