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

Author

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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
    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)

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.

Suggested Citation

  • Huayan Yang & Yu Wang & Huaqi Huang & Lars Gell & Lauri Lehtovaara & Sami Malola & Hannu Häkkinen & Nanfeng Zheng, 2013. "All-thiol-stabilized Ag44 and Au12Ag32 nanoparticles with single-crystal structures," Nature Communications, Nature, vol. 4(1), pages 1-8, December.
    • Handle: RePEc:nat:natcom:v:4:y:2013:i:1:d:10.1038_ncomms3422
    DOI: 10.1038/ncomms3422
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    Cited by:

    1. Claudia Pigliacelli & Angela Acocella & Isabel Díez & Luca Moretti & Valentina Dichiarante & Nicola Demitri & Hua Jiang & Margherita Maiuri & Robin H. A. Ras & Francesca Baldelli Bombelli & Giulio Cer, 2022. "High-resolution crystal structure of a 20 kDa superfluorinated gold nanocluster," Nature Communications, Nature, vol. 13(1), pages 1-8, December.
    2. Xi Kang & Xiao Wei & Xiaokang Liu & Sicong Wang & Tao Yao & Shuxin Wang & Manzhou Zhu, 2021. "A reasonable approach for the generation of hollow icosahedral kernels in metal nanoclusters," Nature Communications, Nature, vol. 12(1), pages 1-7, December.

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