Exploration of Formation and Size-Evolution Pathways of Thiolate-Gold Nanoclusters in the CO-Directed [Au25(SR)18] Synthesis

Jiao Peng, Pu Wang, Bingxin Wang, Lin Xiong, Hengzhi Liu, Yong Pei, Xiao Cheng Zeng

Research output: Contribution to journalArticle

Abstract

An intermolecular association and decarboxylation mechanism is proposed to understand the experimental evidence of the stepwise 2e hopping in the reductant-assisted thiolate-gold cluster synthesis. Based on the newly proposed intermolecular reaction mechanism, a total of 19 molecular-like reaction equations are deduced to account for the bottom-up formation of 2e–8e gold nanoclusters in the CO-directed [Au25(SR)18] synthesis. With these established reaction equations, atomic pathways of three prototype cluster-size evolution reactions are comprehensively explored in the course of [Au25(SR)18] synthesis, namely, the conversion of 0e homoleptic Au(I)-SR complexes to the 2e intermediate Au15(SR)13 cluster, the size-evolution of 2e Au15(SR)13 cluster to the 4e–8ecluster (stepwise 2e-hopping), and the isoelectronic addition reaction of [Au23(SR)16] to the [Au25(SR)18]. The studies reveal that the CO can combine with the Au(I)-complex to form [Aux(SR)x-COOH] species in the alkaline condition, which acts as the active precursors in the 2e hopping cluster-size evolution process. Lastly, as a conceptual extension of the mechanistic studies of the CO-reduction system, a similar intermolecular reaction mechanism is proposed for the 2e reduction in the conventional “NaBH4 reduction” system.

Original languageEnglish (US)
JournalSmall
DOIs
StateAccepted/In press - 2020

Keywords

  • 2e− hopping, cluster-size evolution reactions
  • nucleation mechanisms
  • thiolate-gold nanoclusters

ASJC Scopus subject areas

  • Biotechnology
  • Biomaterials
  • Chemistry(all)
  • Materials Science(all)

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