Ligand-partially-protected metal-chalcogenide supertetrahedral clusters

Abstract

The types and quantities of surface ligands used in the synthesis of nanomaterials play a dominant role in determining their physical and chemical properties, and this situation likewise occurs in metal-chalcogenide supertetrahedral clusters (MCSCs). The MCSCs are mainly categorized into ligand-fully-protected MCSCs and ligand-free ones according to the surface ligand situation. However, ligand-partially-protected MCSCs are rarely reported. In this study, a facile synthetic strategy was proposed to create ligand-partially-protected MCSCs through the pyrolysis of the S–S or Se–Se bond of disulfide organic ligands in a solvothermal procedure, and a series of Pn-type MCSCs with their surface partially protected by thiophenol ligands (ISC-24-MnSnS: 10(3,5-DMPH⁺)·[Mn₄Sn₄S₁₇]¹⁰⁻·4H₂O; ISC-25-MnSnS-SPh: 7(3,5-DMPH⁺)·Mn₄Sn₄S₁₄(SPh)₃⁷⁻·H₂O; ISC-26-MnSnSeCl-SePh: 5.2(3,5-DMPH⁺)·Mn₄Sn₄Se_12.2Cl_0.8(SePh)₄^5.2−·0.8(3,5-DMP)·4H₂O; ISC-26-MnSnSeS-SPh: 6(3,5-DMPH⁺)·Mn₄Sn₄Se₁₂S(SPh)₄⁶⁻·(3,5-DMP)·4H₂O) were obtained. This work could lay a foundation for the synthesis of ligand-partially-protected MCSCs and other partially-protected nanomaterials through the cleavage of disulfide bonds in organic ligands.