Abstract: | The reaction of {(HNEt3)2Ag10(tBuC6H4S)12]}n, Ag2O, Na2MoO4, and m‐methoxybenzoic acid (Hmbc) in CH3OH/CH2Cl2 led to yellow crystals of Ag4S4 (MoO4)5@Ag66] (SD/Ag70b; SD=SunDi) only, while in the presence of DMF, additional dark‐red crystals of Ag10@ (MoO4)7@Ag60] (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 Ag10 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 Ag10 kernel originates from a reduction reaction during the self‐assembly process that involves DMF. This work provides the structural information of a unique Ag10 kernel (five fused Ag4 tetrahedra) and paves an avenue to trap elusive silver species with hierarchical multi‐shell silver nanocluster assemblies with the help of anion templates. |