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

In metal nanoclusters (NCs), the kernel geometry and the nature of the surface protecting ligands are very crucial for their structural stability and properties. The synthesis and structural elucidation of Ag NCs is challenging because the zerovalent oxidation state of Ag is very reactive and prone to oxidization. Here, we report the NC [Ag₅₀S₁₃(StBu)₂₀][CF₃COO]₄ with a hexagonal close-packed (hcp) cagelike Ag₁₄ kernel. A truncated cubic shell and an octahedral shell encapsulate the hcp-layered kernel via an interstitial S²⁻ anionic shell to form an Ag₃₆ Keplerian outer shell of the NC. A theoretical study indicates the stability of this NC in its 4+ charge state and the charge distribution between the kernel and Keplerian shell. The unprecedented electronic structure facilitates its application toward sustainable photoresponse properties. The new insights into this novel Ag NC kernel and Keplerian shell structure may pave the way to understanding the unique structure and developing electronic structure-based applications.