All-thiol-stabilized Ag44 and Au12Ag32 nanoparticles with single-crystal structures

Huayan Yang, Yu Wang, Huaqi Huang, Lars Gell, Lauri Lehtovaara, Sami Malola, Hannu Häkkinen () and Nanfeng Zheng ()
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Huayan Yang: State Key Laboratory for Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, College of Chemistry and Chemical Engineering, Xiamen University
Yu Wang: State Key Laboratory for Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, College of Chemistry and Chemical Engineering, Xiamen University
Huaqi Huang: State Key Laboratory for Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, College of Chemistry and Chemical Engineering, Xiamen University
Lars Gell: Nanoscience Center, University of Jyväskylä
Lauri Lehtovaara: Nanoscience Center, University of Jyväskylä
Sami Malola: Nanoscience Center, University of Jyväskylä
Hannu Häkkinen: Nanoscience Center, University of Jyväskylä
Nanfeng Zheng: State Key Laboratory for Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, College of Chemistry and Chemical Engineering, Xiamen University

Nature Communications, 2013, vol. 4, issue 1, 1-8

Abstract: Abstract Noble metal nanoparticles stabilized by organic ligands are important for applications in assembly, site-specific bioconjugate labelling and sensing, drug delivery and medical therapy, molecular recognition and molecular electronics, and catalysis. Here we report crystal structures and theoretical analysis of three Ag44(SR)30 and three Au12Ag32(SR)30 intermetallic nanoclusters stabilized with fluorinated arylthiols (SR=SPhF, SPhF2 or SPhCF3). The nanocluster forms a Keplerate solid of concentric icosahedral and dodecahedral atom shells, protected by six Ag2(SR)5 units. Positive counterions in the crystal indicate a high negative charge of 4− per nanoparticle, and density functional theory calculations explain the stability as an 18-electron superatom shell closure in the metal core. Highly featured optical absorption spectra in the ultraviolet–visible region are analysed using time-dependent density functional perturbation theory. This work forms a basis for further understanding, engineering and controlling of stability as well as electronic and optical properties of these novel nanomaterials.

Date: 2013
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DOI: 10.1038/ncomms3422

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