Beyond The Sphere. Au₂₀(PR₃)₈ as a Spherical Aromatic Cuboctahedron Cluster

The icosahedral Au 13 5+ core is a recurrent building block in ligand‐protected gold clusters involving an 8‐cluster electron 1S 2 1P 6 electronic shell. Such a prototypical structure enables a spherical aromatic behavior as given by long‐range magnetic shielding. Recently, the Au 20 ( t Bu 3 P) 8 cluster featuring a contrasting cuboctahedral core with formally neutral gold atoms appears as a novel core architecture with the potential to be considered as another potential building block towards functional nanostructures. Here, we explore the ligand‐core interaction and spherical aromatic characteristics of Au 20 ( t Bu 3 P) 8 , in order to provide a direct connection to classical icosahedral spherical aromatic compounds, now involving a cuboctahedral core structure. Such characteristics suggest rationalization of their robustness in terms of certain electron counts, enabling a shielding cone property in ligand‐protected metallic clusters, which favors bridging organic and inorganic planar/spherical aromatic species towards the unification of the aromaticity concept and designing guidelines for further achievements.