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. ...
Publication in research information system
MetadataShow full item record
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. ...
Showing items with similar title or keywords.
Surface Coordination of Multiple Ligands Endows N‐Heterocyclic Carbene‐Stabilized Gold Nanoclusters with High Robustness and Surface Reactivity Shen, Hui; Xu, Zhen; Hazer, Maryam Sabooni Asre; Wu, Qingyuan; Peng, Jiang; Qin, Ruixuan; Malola, Sami; Teo, Boon K.; Häkkinen, Hannu; Zheng, Nanfeng (Wiley-VCH Verlag, 2021)Deciphering the molecular pictures of the multi-component and non-periodic organic-inorganic interlayer is a grand technical challenge. Here we show that the atomic arrangement of hybrid surface ligands on metal nanoparticles ...
Hyeon, Taeghwan; Bootharaju, Megalamane S.; Lee, Sanghwa; Deng, Guocheng; Malola, Sami; Baek, Woonhyuk; Häkkinen, Hannu; Zheng, Nanfeng (Wiley-VCH Verlag, 2021)Although atomically precise metalloid nanoclusters (NCs) of identical size with distinctly different molecular structures are highly desirable to understand the structural effects on the intriguing optical and photophysical ...
Sokolowska, Karolina; Malola, Sami; Lahtinen, Manu; Saarnio, Ville; Permi, Perttu; Koskinen, Katariina; Jalasvuori, Matti; Häkkinen, Hannu; Lehtovaara, Lauri; Lahtinen, Tanja (American Chemical Society, 2019)Water-soluble gold nanoclusters with well-defined molecular structures and stability possess particular biophysical properties making them excellent candidates for biological applications as well as for fundamental ...
Shen, Hui; Wang, Lingzheng; López-Estrada, Omar; Hu, Chengyi; Wu, Qingyuan; Cao, Dongxu; Malola, Sami; Teo, Boon K.; Häkkinen, Hannu; Zheng, Nanfeng (Springer, 2021)Copper-hydrides have been intensively studied for a long time due to their utilization in a variety of technologically important chemical transformations. Nevertheless, poor stability of the species severely hinders its ...
Sabooni Asre Hazer, Maryam; Malola, Sami; Häkkinen, Hannu (Royal Society of Chemistry, 2022)The use of metal nanoclusters is strongly reliant on their size and configuration; hence, studying the potential isomers of a cluster is extremely beneficial in understanding their performance. In general, the prediction ...