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) {(Ag3PO4)8}, reminiscent of the Ag3PO4 photocatalyst. The SOC is capped by six interstitial sulfur atoms, giving a unique anionic cluster [Ag6@{(Ag3PO4)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@{(Ag3PO4)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 Ag3PO4, and offers a fresh template strategy for the synthesis of silver NCs with high symmetry. A giant globular 102 Ag atom nanocluster has been isolated by a templating approach. The nanocluster features an unprecedented sodalite‐type silver orthophosphate cluster (SOC) stabilized in a rare 60‐Ag rhombicosidodecahedron. This is a reminder of the key role of the SOC as a molecular analogue of the important Ag3PO4 semiconducting material.