A Sodalite‐Type Silver Orthophosphate Cluster in a Globular Silver Nanocluster

The synthesis and structure of a giant 102-silver-atom nanocluster (NC) 1 is presented. X-ray structural analysis reveals that 1 features a multi-shelled metallic core of Ag6 @Ag24 @Ag60 @Ag12 . An octahedral Ag6 core is encaged by a truncated octahedral Ag24 shell. The Ag24 shell is composed of a hitherto unknown sodalite-type silver orthophosphate cluster (SOC) {(Ag3 PO4 )8 }, reminiscent of the Ag3 PO4 photocatalyst. The SOC is capped by six interstitial sulfur atoms, giving a unique anionic cluster [Ag6 @{(Ag3 PO4 )8 }S6 ]6- , which functions as an intricate polyhedral template with abundant surface O and S atoms guiding the formation of a rare rhombicosidodecahedral Ag60 shell. An array of 6 linear Ag2 staples further surround this Ag60 shell. [Ag6 @{(Ag3 PO4 )8 }S6 ]6- is an unusual Ag-based templating anion to induce the assembly of a SOC within silver NC. This finding provides molecular models for bulk Ag3 PO4 , and offers a fresh template strategy for the synthesis of silver NCs with high symmetry.