Synthesis and Characterization of a Rare Transition-Metal Oxothiostannate and Investigation of Its Photocatalytic Properties

Abstract

The new transition-metal oxothiostannate [Ni(cyclen)(H₂O)₂]₄[Sn₁₀S₂₀O₄]·∼13H₂O (1) was prepared under hydrothermal conditions using Na₄SnS₄·14H₂O as the precursor in the presence of [Ni(cyclen)(H₂O)₂](ClO₄)₂·H₂O. Compound 1 comprises the [Sn₁₀S₂₀O₄]^8- anion constructed by the T3-type supertetrahedron [Sn₁₀S₂₀] and the [Sn₁₀O₄] anti-T2 cluster. Channels host the H₂O molecules, and the sample can be reversibly dehydrated and rehydrated without significantly affecting the crystallinity of the material. ¹¹⁹Sn NMR spectroscopy of an aqueous solution of Na₄SnS₄·14H₂O evidences that between 25 and 120 °C only [SnS₄]^4- and [Sn₂S₆]^4- anions are present. In further experiments, hints were found that the formation of tin oxosulfide ions depends on the Ni²⁺-centered complexes. Compound 1 exhibits promising photocatalytic properties for the visible-light-driven hydrogen evolution reaction, with 18.7 mmol·g^-1 H₂ being evolved after 3 h.