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

• Published in: Small (Weinheim an der Bergstrasse, Germany) p. e2403520
• Main Authors: Liu, Hengzhi, Huang, Baoyu, Shao, Youyuan, Pei, Yong
• Format: Journal Article
• Language: English
• Published: Germany 07.08.2024
• Subjects: homo metal exchange; hetero metal exchange; ab initio molecular dynamics simulation; metal–thiolate complexes; noble metal nanoclusters
• ISSN: 1613-6810; 1613-6829
• DOI: 10.1002/smll.202403520

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