Size Evolution of the 2e-Superatom in Ligand-Protected Au Nanoclusters: Au2-(AuL)1–12 (L = Cl, SH, SCH3, PH2, and P(CH3)2)

Abstract

Ligand-protected gold (Au-L) nanoclusters have attracted much attention due to their unique properties, and the superatom concept as a significantly well-known concept to explain the electronic stability was suggested. Although there has been a lot of major progress in this field, size evolution of the superatom is still little known because of limited experimental data. To give a direct and overall view of size evolution of the superatom in Au-L clusters, the Au2-(AuL)1–12 (L = Cl, SH, SCH3, PH2, P(CH3)2) system is taken as a test case. The global minimum geometries are studied by using a method combining the genetic algorithm with density functional theory. The gold cores in these structures consist of Au3, Au4, Au5, and Au6 2e-superatoms protected by staple motifs. The 2e-superatoms were confirmed by chemical bonding analysis using the adaptive natural density partitioning method. The aromatic properties of the center of these compounds have been explored by the nucleus-independent chemical shift metho...