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) {(Ag3PO4)(8)}, reminiscent of the Ag3PO4 photocatalyst. The SOC is capped by six interstitial sulfur atoms, giving a unique anionic cluster [Ag-6@{(Ag3PO4)(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@{(Ag3PO4)(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 Ag3PO4, and offers a fresh template strategy for the synthesis of silver NCs with high symmetry.