Doping Effects in the Thiolate-Protected Gold Nanoclusters from the Perspective of Balance Between Ligands and the Core

Abstract

The atomically precise method has become an important technique for adjusting the core of thiolate-protected gold nanoclusters to improve biological, physical, and chemical properties. But, the doping effect on the structural stability across different elements has not been modeled within the scope of a bigger picture. Therefore, in this work, the H2S–nanoalloy complexes with different doping metal atoms have been investigated to elucidate the effects of the dopant on the structures. Indicated by simplified model complexes and density functional theory (DFT) simulation results, the zinc group atoms as dopants may be influenced by surrounded gold atoms, and binding to the thiolate units is enhanced by the addition of gold atoms. The reactivity of the zinc group atoms may be activated by a gold nanocluster. The simulated zinc group data when combined with the gold group and platinum group data can be summarized in the perspective of balance between the ligand–core binding and core cohesive energies. Most dopants move the modeled nanoclusters away from the balance, especially when the metal atom replaced the gold atom in gold–sulfur bindings. Besides, when cores of the nanoclusters are dominated by gold atoms, the dopants may achieve “saturation” such that the balance in the doped clusters may be corrected. This work provides a simple profile to understand the internal shift of the structure introduced by the atomically precise method.