Unveiling Complex Structural Features of Thiolate-Protected Gold Nanoclusters: From Internal Core to External “Staple” Motifs and Overall Charge States

The revelation of numerous thiolate-protected gold nanocluster (TP-AuNCs) structures, achieved through a blend of theoretical predictions and experimental detection/validation, presents a vast amount of data for understanding the structural evolution of these nanoclusters. Typically, these clusters featured an internal gold core surrounded by external “staple” motifs SR[Au(SR)]_x (x = 0, 1, 2, 3, ...) at various charge states. In this Account, we outline our Grand Unified Model (GUM) that elucidates the growth mechanism of the internal gold core, the bonding nature of outer “staple” motifs, and a ring model illuminating the intricate interfacial interactions between the motifs and the internal gold core, as well as a simple rule governing charge states.