Synthesis, crystal structure and luminescence of [(CH 3 ) 3 S] 2 ZrCl 6

The current work reports on the synthesis, crystal structure and optoelectronic properties of (Me₃S)₂ZrCl₆, prepared by reacting the solid precursors (Me₃S)Cl and ZrCl₄ in pyrex tubes at 150 °C under vacuum. According to X-ray powder diffraction and Rietveld analysis, (Me₃S)₂ZrCl₆ crystallizes in the cubic space group Pa-3 (No. 205) with a = 12.4664(1) Å. The crystal structure consists of isolated trigonal pyramidal trimethylsulfonium cations and octahedral [ZrCl₆]^2- anions with weak hydrogen bonds among them and no signs of structural disorder. This 0D-material is stable in air and dissolves in water and dimethylformamide. Raman spectroscopy shows characteristic vibrational modes for the organic and inorganic moieties over the frequency range of 5–3200 cm⁻¹. UV-Vis spectroscopy reveals a large band gap of 5.1 eV and a broadband luminescence with emission maximum at 465 nm in the solid state. The luminescent properties of (Me₃S)₂ZrCl₆ are discussed and compared with those of similar inorganic or metal-organic compounds.