Core Modulation of 70‐Nuclei Core‐Shell Silver Nanoclusters

The reaction of {(HNEt3)2[Ag10(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. The third layer is the charm: The construction of three‐layer shell structures of hybrid silver nanoclusters is reported. While the majority of the silver atoms usually makes up the outermost shell, an unprecedented Ag10 cluster forms in the innermost shell if DMF is present during synthesis. The work presents an approach to trap elusive embryonic silver species in nanocluster assemblies.