Hetero and Homo Metal Exchange of Au 25 (SR) 18 - and Ag 25 (SR) 18 - Clusters with Metal-Thiolate Complexes: Ab Initio Molecular Dynamics Simulation Studies.

The hetero and homo metal exchange of Au 25 (SR) 18 - and Ag 25 (SR) 18 - nanoclusters with metal-thiolate (M-SR) complexes (Au I (SR), Ag I (SR), Cu I (SR), and Cu II (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.