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Solubility‐Driven Isolation of a Metastable Nonagold Cluster with Body‐Centered Cubic Structure by Shen, Hui; Selenius, Elli; Ruan, Pengpeng; Li, Xihua; Yuan, Peng; Lopez-Estrada, Omar; Malola, Sami; Lin, Shuichao; Teo, Boon K.; Häkkinen, Hannu; Zheng, Nanfeng is a Chemistry article available to read on EtoBox.

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## Abstract The conventional synthetic methodology for atomically precise gold nanoclusters by using reduction in solution offers only the thermodynamically most stable nanoclusters. Herein, a solubility‐driven isolation strategy is reported to access 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 measurements, 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 although 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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Author

Shen, Hui; Selenius, Elli; Ruan, Pengpeng; Li, Xihua; Yuan, Peng; Lopez-Estrada, Omar; Malola, Sami; Lin, Shuichao; Teo, Boon K.; Häkkinen, Hannu; Zheng, Nanfeng

Publisher

Wiley

Published

2020

Language

EN

Field

Chemistry (Physical Sciences)