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

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