Rhombicuboctahedral Ag100 : Four-Layered Octahedral Silver Nanocluster Adopting the Russian Nesting Doll Model.

Precise atomic structure of metal nanoclusters (NCs) is fundamental for elucidating the structure-property relationships and the inherent size-evolution principles. Reported here is the largest known FCC-based (FCC=face centered cubic) silver nanocluster, [Ag100 (SC6 H3 3,4 F2 )48 (PPh3 )8 ]- : the first all-octahedral symmetric nesting Ag nanocluster with a four-layered Ag6 @Ag38 @Ag48 S24 @Ag8 S24 P8 structure, consistent symmetry elements, and a unique rhombicuboctahedral morphology distinct from theoretical predictions and previously reported FCC-based Ag clusters. DFT studies revealed extensive interlayer interactions and degenerate frontier orbitals. The FCC-based Russian nesting doll model constitutes a new platform for the study of the size-evolution principles of Ag NCs.