Chiral Inversion of Au40(SR)24 Nanocluster Driven by Rotation of Gold Tetrahedra in the Kekulé-like Core

Studying the chiral characteristics and chiral inversion mechanisms of gold nanoclusters is important to promote their applications in the field of chiral catalysis and chiral recognition. Herein, we investigated the chiral inversion process of the Au₄₀(SR)₂₄ nanocluster and its derivatives using density functional theory calculations. The results showed that the chiral inversion process can be achieved by rotation of tetrahedra units in the gold core without breaking the Au–S bond. This work found that Au₄₀ nanoclusters protected by different ligands have different chiral inversion mechanisms, and the difference is mainly attributable to the steric effects of the ligands. Moreover, the chiral inversion of the derivative clusters (Au₃₄, Au₂₈, and Au₂₂) of the Au₄₀ nanocluster can also be accomplished by the rotation of the Au₄ tetrahedra units in the gold core. The energy barrier in the chiral inversion process of gold nanoclusters increases with the decrease of Au₄ tetrahedra units in the gold core. This work identifies a chiral inversion mechanism with lower reaction energy barriers and provided a theoretical basis for the study of gold nanocluster chirality.