Heterometallic sulfide cluster [Ag6Sn6S20]10 −: Solvothermal syntheses and characterizations of silver thiostannates with lanthanide complex counter cations

•Lanthanide silver thiostannates 1–3 were prepared using solvothermal methods.•The novel [Ag6Sn6S20]10 − cluster is obtained with Ln complex counter cations.•1–3 exhibit optical band gaps between 2.18 and 2.47 eV.

Novel organic hybrid silver thiostannates [Hen]4[Ln(en)4]2[Ag6Sn6S20]·3en (Ln = Er, 1; Tm, 2; Yb, 3) were prepared by the reactions of Ln2O3, Ag, Sn and S in ethylenediamine (en) under solvothermal conditions. Six SnS4 tetrahedra and six AgS3 triangles are connected into the heterometallic sulfide cluster [Ag6Sn6S20]10 − via edge-sharing. In the [Ag6Sn6S20]10 − cluster, a hexanuclear Ag6S6 core is enclosed by two Sn3S10 fragments. The Ag6S6 core is the first As–S cluster stabilized by inorganic SnS4 ligands. In 1–3, all Ln3 + ions are in 8-fold coordination environments that involved four bidentate en ligands, forming bicapped trigonal prisms. Compounds 1–3 show well-defined absorption edges with band gaps in the range of 2.18–2.47 eV.

Graphical abstractNovel silver thiostannates [Hen]4[Ln(en)4]2[Ag6Sn6S20]·3en (Ln = Er, 1; Tm, 2; Yb, 3) were prepared by solvothermal methods. Compounds 1–3 are the first examples of ternary silver-chalcogenidostannates containing Ln complex counter cations.Figure optionsDownload full-size imageDownload as PowerPoint slide