TY - JOUR
T1 - Exploration of Formation and Size-Evolution Pathways of Thiolate-Gold Nanoclusters in the CO-Directed [Au25(SR)18]− Synthesis
AU - Peng, Jiao
AU - Wang, Pu
AU - Wang, Bingxin
AU - Xiong, Lin
AU - Liu, Hengzhi
AU - Pei, Yong
AU - Zeng, Xiao Cheng
N1 - Funding Information:
Y.P. acknowledges financial support by National Natural Science Foundation of China (91961121, 21773201, and 21422305) and the project of innovation team of the ministry of education (IRT_17R90).
Publisher Copyright:
© 2020 Wiley-VCH GmbH
PY - 2021/7/8
Y1 - 2021/7/8
N2 - 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−–8e−cluster (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.
AB - 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−–8e−cluster (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.
KW - 2e− hopping, cluster-size evolution reactions
KW - nucleation mechanisms
KW - thiolate-gold nanoclusters
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U2 - 10.1002/smll.202000627
DO - 10.1002/smll.202000627
M3 - Article
C2 - 32761785
AN - SCOPUS:85089010302
SN - 1613-6810
VL - 17
JO - Small
JF - Small
IS - 27
M1 - 2000627
ER -