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 Ag 6 @Ag 24 @Ag 60 @Ag 12 . An octahedral Ag 6 core is encaged by a truncated octahedral Ag 24 shell. The Ag 24 shell is composed of a hitherto unknown sodalite‐type silver orthophosphate cluster (SOC) {(Ag 3 PO 4 ) 8 }, reminiscent of the Ag 3 PO 4 photocatalyst. The SOC is capped by six interstitial sulfur atoms, giving a unique anionic cluster [Ag 6 @{(Ag 3 PO 4 ) 8 }S 6 ] 6− , which functions as an intricate polyhedral template with abundant surface O and S atoms guiding the formation of a rare rhombicosidodecahedral Ag 60 shell. An array of 6 linear Ag 2 staples further surround this Ag 60 shell. [Ag 6 @{(Ag 3 PO 4 ) 8 }S 6 ] 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 Ag 3 PO 4 , and offers a fresh template strategy for the synthesis of silver NCs with high symmetry.