Nuclearity enlargement from [PW9O34@Ag51] to [(PW9O34)2@Ag72] and 2D and 3D network formation driven by bipyridines

Zhi Wang, Yan-Jie Zhu, Ying-Zhou Li, Gui-Lin Zhuang, Ke-Peng Song, Zhi-Yong Gao, Jian-Min Dou, Mohamedally Kurmoo, Chen-Ho Tung and Di Sun ()
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Zhi Wang: Shandong University
Yan-Jie Zhu: Shandong University
Ying-Zhou Li: Qilu University of Technology (Shandong Academy of Science)
Gui-Lin Zhuang: Zhejiang University of Technology
Ke-Peng Song: Shandong University
Zhi-Yong Gao: Henan Normal University
Jian-Min Dou: Liaocheng University
Mohamedally Kurmoo: Institut de Chimie de Strasbourg
Chen-Ho Tung: Shandong University
Di Sun: Shandong University

Nature Communications, 2022, vol. 13, issue 1, 1-9

Abstract: Abstract The structural transformations of metal nanoclusters are typically quite complex processes involving the formation and breakage of several bonds, and thus are challenging to study. Herein, we report a case where two lacunary Keggin polyoxometallate templated silver single-pods [PW9O34@Ag51] (SD/Ag51b) fuse to a double-pod [(PW9O34)2@Ag72] by reacting with 4,4’-bipyridine (bipy) or 1,4-bis(4-pyridinylmethyl)piperazine (pi-bipy). Their crystal structures reveal the formation of a 2D 44-sql layer (SD/Ag72a) with bipy and a 3D pcu framework (SD/Ag72c) with pi-bipy. The PW9O349− retains its structure during the cluster fusion and cluster-based network formation. Although the two processes, stripping of an Ag-ligands interface followed by fusion, and polymerization, are difficult to envisage, electrospray ionization mass spectrometry provides enough evidences for such a proposal to be made. Through this example, we expect the structural transformation to become a powerful method for synthesizing silver nanoclusters and their infinite networks, and to evolve from trial-and-error to rational.

Date: 2022
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DOI: 10.1038/s41467-022-29370-w

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