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

In metal nanoclusters (NCs), the kernel geometry and the nature of thesurface protecting ligands are very crucial for their structural stability and properties. Thesynthesis and structural elucidation of Ag NCs is challenging because the zerovalentoxidation state of Ag is very reactive and prone to oxidization. Here, we report the NC[Ag50S13(StBu)20][CF3COO]4with a hexagonal close-packed (hcp) cagelike Ag14kernel. Atruncated cubic shell and an octahedral shell encapsulate thehcp-layered kernel via aninterstitial S2-anionic shell to form an Ag36Keplerian outer shell of the NC. A theoreticalstudy indicates the stability of this NC in its 4+ charge state and the charge distributionbetween the kernel and Keplerian shell. The unprecedented electronic structure facilitates its application toward sustainablephotoresponse properties. The new insights into this novel Ag NC kernel and Keplerian shell structure may pave the way tounderstanding the unique structure and developing electronic structure-based application

Automated summary

The geometry of the kernel and the nature of the surface protecting ligands are crucial for the stability and properties of metal nanoclusters. This study presents a new type of silver nanocluster with a hexagonal close-packed (hcp) core and truncated cubic and octahedral shells. The theoretical analysis suggests that the nanocluster is stable in its 4+ charge state and has an unique electronic structure that facilitates sustainable photoresponse properties.