Abstract
AbstractThe synthesis and structure of a giant 102‐silver‐atom nanocluster (NC)1is presented. X‐ray structural analysis reveals that1features a multi‐shelled metallic core of Ag6@Ag24@Ag60@Ag12. An octahedral Ag6core is encaged by a truncated octahedral Ag24shell. The Ag24shell is composed of a hitherto unknown sodalite‐type silver orthophosphate cluster (SOC) {(Ag3PO4)8}, reminiscent of the Ag3PO4photocatalyst. 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 Ag60shell. An array of 6 linear Ag2staples further surround this Ag60shell. [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.
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