Solubility‐Driven Isolation of a Metastable Nonagold Cluster with Body‐Centered Cubic Structure
Shen, H., Selenius, E., Ruan, P., Li, X., Yuan, P., Lopez-Estrada, O., Malola, S., Lin, S., Teo, B. K., Häkkinen, H., & Zheng, N. (2020). Solubility‐Driven Isolation of a Metastable Nonagold Cluster with Body‐Centered Cubic Structure. Chemistry : A European Journal, 26(38), 8465-8470. https://doi.org/10.1002/chem.202001753
Published inChemistry : A European Journal
© 2020 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim
The conventional synthetic methodology of atomically precise gold nanoclusters using reduction in solutions offers only thermodynamically most stable nanoclusters. We report herein a solubility‐driven isolation strategy to access the synthesis of a metastable gold cluster. The cluster, with the composition of [Au 9 (PPh 3 ) 8 ] + ( 1 ), displays an unusual, nearly perfect body‐centered‐cubic (bcc) structure. As revealed by ESI‐MS and UV/Vis measurement, the cluster is metastable in solution and converts to the well‐known [Au 11 (PPh 3 ) 8 Cl 2 ] + ( 2 ) within just 90 min. DFT calculations revealed that while both 1 and 2 are eight‐electron superatoms, there is a driving force to convert 1 to 2 as shown by the increased cohesion and larger HOMO‐LUMO energy gap of 2 . The isolation and crystallization of the metastable gold cluster were achieved in a biphasic reaction system in which reduction of gold precursors and crystallization of 1 took place concurrently. This synthetic protocol represents a successful strategy for investigations of other metastable species in metal nanocluster chemistry. ...
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Related funder(s)Academy of Finland
Funding program(s)Research costs of Academy Professor, AoF; Academy Programme, AoF
Additional information about fundingWe thank the National Key R&D Program of China (2017YFA0207302) and the NSF of China (21890752, 21731005, 21721001) for financial support. The computational work in the University of Jyväskylä was supported by the Academy of Finland (grants 29421, 319208, 315549,and through HH’s Academy Professorship). H.H. acknowledges support from China’s National Innovation and Intelligence Introduction Base visitor program. E.S. acknowledges the Emil Aaltonen Foundation for a PhD study grant. The computations were made at the CSC supercomputing center in Finland and as part of a PRACE project in the Barcelona Supercomputing Center. ...
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