Core Modulation of 70-Nuclei Core-Shell Silver Nanoclusters

The reaction of {(HNEt3)(2)[Ag-10(tBuC(6)H(4)S)(12)]}(n), Ag2O, Na2MoO4, and m-methoxybenzoic acid (Hmbc) in CH3OH/CH2Cl2 led to yellow crystals of [Ag4S4 (MoO4)(5)@Ag-66] (SD/Ag70b; SD=SunDi) only, while in the presence of DMF, additional dark-red crystals of [Ag-10@ (MoO4)(7)@Ag-60] (SD/Ag70a) were obtained. SD/Ag70b consists of five MoO42- ions wrapped by a shell of 66 Ag atoms, while SD/Ag70a contains a rare Ag-10 kernel consisting of five tetrahedra sharing faces and edges, surrounded by seven MoO42- ions enclosed in a shell of 60 Ag atoms. The formation of the Ag-10 kernel originates from a reduction reaction during the self-assembly process that involves DMF. This work provides the structural information of a unique Ag-10 kernel (five fused Ag-4 tetrahedra) and paves an avenue to trap elusive silver species with hierarchical multi-shell silver nanocluster assemblies with the help of anion templates.