Hetero and Homo Metal Exchange of Au25(SR)18− and Ag25(SR)18− Clusters with Metal–Thiolate Complexes: Ab Initio Molecular Dynamics Simulation Studies

Abstract

AbstractThe hetero and homo metal exchange of Au25(SR)18− and Ag25(SR)18− nanoclusters with metal–thiolate (M–SR) complexes (AuI(SR), AgI(SR), CuI(SR), and CuII(SR)2) are studied using ab initio molecular dynamics (AIMD) simulations. The AIMD simulation results unveil that the M–SR complexes directly displace Au(SR) or Ag(SR) units on the gold or silver core surface through an “anchoring effect”. The whole process of metal‐exchange reactions can be divided into three steps, including the adsorption of M–SR complexes on clusters, the formation of new staple motif, and the displacement of Au(SR) or Ag(SR) units by M–SR complexes. The key role of sulfur atoms in metal exchange reactions in M–SR complexes is revealed, which facilitates formation of new staple motifs and doping of M–SR complexes into gold and silver cores. This work provides a theoretical basis for further exploring the metal exchange reaction between noble metal nanoclusters and metal–thiolate complexes, as well as the isotope exchange reactions.