Abstract

Nowadays, the use of sulfur‐based ligands to modify gold‐based materials has become a common trend. Here, we present a theoretical exploration of the modulation of the chalcogenides‐gold interaction strength, using sulfur, selenium, and tellurium as anchor atoms. To characterize the chalcogenide‐gold interaction, we designed a nanocluster of 42 gold atoms (Au42) to model a gold surface (111) and a series of 60 functionalized phenyl‐chalcogenolate ligands to determine the ability of electron‐donor and ‐withdrawing groups to modulate the interaction. The analysis of the interaction was performed by using energy decomposition analysis (EDA), non‐covalent interactions index (NCI), and natural population analysis (NPA) to describe the charge transfer processes and to determine data correlation analyses. The results revealed that the magnitudes of the interaction energies increase following the order S < Se < Te, where this interaction strength can be augmented by electron‐donor groups, under the donor‐acceptor character the chalcogen–gold interaction. We also found that the functionalization in meta position leads to better control of the interaction strength than the ortho substitution due to the steric and inductive effects involved when functionalized in this position.