Liu Hengzhi, Huang Baoyu, Shao Youyuan, Pei Yong
Department of Chemistry, Key Laboratory of Environmentally Friendly Chemistry and Applications of Ministry of Education, Xiangtan University, Xiangtan, 411105, China.
Hunan Province Key Laboratory of Environmental Catalysis and Waste Recycling, College of Materials and Chemical Engineering, Hunan Institute of Engineering, Xiangtan, 411104, P. R. China.
Small. 2024 Nov;20(46):e2403520. doi: 10.1002/smll.202403520. Epub 2024 Aug 7.
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.
利用从头算分子动力学（AIMD）模拟研究了Au(SR)和Ag(SR)纳米团簇与金属硫醇盐（M-SR）配合物（Au(SR)、Ag(SR)、Cu(SR)和Cu(SR)）之间的异质和同质金属交换。AIMD模拟结果表明，M-SR配合物通过“锚定效应”直接取代金或银核表面的Au(SR)或Ag(SR)单元。金属交换反应的整个过程可分为三个步骤，包括M-SR配合物在团簇上的吸附、新主链基序的形成以及M-SR配合物取代Au(SR)或Ag(SR)单元。揭示了硫原子在M-SR配合物金属交换反应中的关键作用，这有助于新主链基序的形成以及M-SR配合物掺杂到金和银核中。这项工作为进一步探索贵金属纳米团簇与金属硫醇盐配合物之间的金属交换反应以及同位素交换反应提供了理论基础。
