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

Abstract

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(SC6H33,4F2)48(PPh3)8]−: the first all‐octahedral symmetric nesting Ag nanocluster with a four‐layered Ag6@Ag38@Ag48S24@Ag8S24P8 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.

The New Ag–S Cluster [Ag50S13(StBu)20][CF3COO]4 with a Unique hcp Ag14 Kernel and Ag36 Keplerian-Shell-Based Structural Architecture and Its Photoresponsivity

“…Over the past few years, the face-centered cubic ( fcc ) core of silver NCs has also attracted deep interest, as it correlates with the macroscopic fcc bulk silver metals. Indeed, several fcc -type kernel structure based NCs have been reported, including Ag 14 , − Ag 15 , Ag 23 , Ag 38 , Ag 46 , , Ag 62 , Ag 63 , Ag 67 , and Ag 100 . However, another type of cubic closed packing, i.e., hexagonal close-packed ( hcp ), is not known to our knowledge.…”

“…Indeed, several fcc-type kernel structure based NCs have been reported, including Ag 14 , 20−22 Ag 15 , 23 Ag 23 , 24 Ag 38 , 25 Ag 46 , 26,27 Ag 62 , 28 Ag 63 , 25 Ag 67 , 29 and Ag 100 . 30 However, another type of cubic closed packing, i.e., hexagonal close-packed (hcp), is not known to our knowledge. It is worth noting that only two reports are available for hcp-based gold NCs: namely, Au 18 (SC 6 H 11 ) 14 31 and Au 30 (S-Adm) 18 .…”

Revealing the chirality origin and homochirality crystallization of Ag14 nanocluster at the molecular level

“…While the last type is rather difficult to access in experiments due to the more subtle influencing factors. As we know, while the silver nanoclusters are more likely to adopt polyhedral structures with high symmetry, such as Ag 180 , Ag 100 , Ag 90 , Ag 63 , Ag 48 , Ag 46 , Ag 40, and Ag 38 [26][27][28][29][30][31] , those with chiral polyhedral cores, however, are rarely reported 32 .…”