Ligand-partially-protected metal-chalcogenide supertetrahedral clusters.

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 P n -type MCSCs with their surface partially protected by thiophenol ligands (ISC-24-MnSnS: 10(3,5-DMPH + )·[Mn 4 Sn 4 S 17 ] 10- ·4H 2 O; ISC-25-MnSnS-SPh: 7(3,5-DMPH + )·Mn 4 Sn 4 S 14 (SPh) 3 7- ·H 2 O; ISC-26-MnSnSeCl-SePh: 5.2(3,5-DMPH + )·Mn 4 Sn 4 Se 12.2 Cl 0.8 (SePh) 4 5.2- ·0.8(3,5-DMP)·4H 2 O; ISC-26-MnSnSeS-SPh: 6(3,5-DMPH + )·Mn 4 Sn 4 Se 12 S(SPh) 4 6- ·(3,5-DMP)·4H 2 O) 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.