Ring Model for Understanding How Interfacial Interaction Dictates the Structures of Protection Motifs and Gold Cores in Thiolate-Protected Gold Nanoclusters

Understanding the effect of interfacial interactions between the protection motifs and gold cores on the stabilities of thiolate-protected gold nanoclusters is still a challenging task. Based on analyses of 95 experimentally crystallized and theoretically predicted thiolate-protected gold nanoclusters, we present a ring model to offer a deeper insight into the interfacial interactions for this class of nanoclusters. In the ring model, all the gold nanoclusters can be generically viewed as a fusion or interlocking of several [Au_m(SR)_n] (m = 4–8, 10, and 12 and 0 ≤ n ≤ m) rings. Guided by the ring model and the grand unified model, a new Au₄₂(SR)₂₆ isomer is predicted, whose total energy is lower than those of two previously crystallized isomers. The ring model offers a mechanistic understanding of the interactions between the protection ligands and gold cores and practical guidance on predicting new gold nanoclusters for future experimental synthesis and confirmation.