Disc‐Like Silver Nanocluster Ag₉₃ Built with Bicapped Hexagonal Prismatic Ag₁₅ and Ino Decahedral Ag₁₃ Units

Abstract The reduction of alkynyl‐silver and phosphine‐silver precursors with a weak reducing reagent Ph 2 SiH 2 led to the formation of a novel silver nanocluster [Ag 93 (PPh 3 ) 6 (C≡CR) 50 ] 3+ (R=4‐CH 3 OC 6 H 4 ), which is the largest structurally characterized cluster of clusters. This disc‐shaped cluster has a Ag 69 kernel consisting of a bicapped hexagonal prismatic Ag 15 unit wrapped by six Ino decahedra through edge‐sharing. This is the first time that Ino decahedra are used as a building block to assemble a cluster of clusters. Moreover, the central silver atom has a coordination number of 14, which is the highest in metal nanoclusters. This work provides a diverse metal packing pattern in metal nanoclusters, which is helpful for understanding metal cluster assembling mechanisms.