Co-crystallization of atomically precise metal nanoparticles driven by magic atomic and electronic shells

Juanzhu Yan, Sami Malola, Chengyi Hu, Jian Peng, Birger Dittrich, Boon K. Teo, Hannu Häkkinen (), Lansun Zheng and Nanfeng Zheng ()
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Juanzhu Yan: Xiamen University
Sami Malola: University of Jyväskylä
Chengyi Hu: Xiamen University
Jian Peng: Xiamen University
Birger Dittrich: Universitätsstrasse 1
Boon K. Teo: Xiamen University
Hannu Häkkinen: University of Jyväskylä
Lansun Zheng: Xiamen University
Nanfeng Zheng: Xiamen University

Nature Communications, 2018, vol. 9, issue 1, 1-8

Abstract: Abstract This paper reports co-crystallization of two atomically precise, different-size ligand-stabilized nanoclusters, a spherical (AuAg)267(SR)80 and a smaller trigonal-prismatic (AuAg)45(SR)27(PPh3)6 in 1:1 ratio, characterized fully by X-ray crystallographic analysis (SR = 2,4-SPhMe2). The larger cluster has a four concentric-shell icosahedral structure of Ag@M12@M42@M92@Ag120(SR)80 (M = Au or Ag) with the inner-core M147 icosahedron observed here for metal nanoparticles. The cluster has an open electron shell of 187 delocalized electrons, fully metallic, plasmonic behavior, and a zero HOMO-LUMO energy gap. The smaller cluster has an 18-electron shell closing, a notable HOMO-LUMO energy gap and a molecule-like optical spectrum. This is the first direct demonstration of the simultaneous presence of competing effects (closing of atom vs. electron shells) in nanocluster synthesis and growth, working together to form a co-crystal of different-sized clusters. This observation suggests a strategy that may be helpful in the design of other nanocluster systems via co-crystallization.

Date: 2018
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DOI: 10.1038/s41467-018-05584-9

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