Jump to main content
Jump to site search


Diphosphine-Protected Ultrasmall Gold Nanoclusters: Opened Icosahedral Au13 and Heart-Shaped Au8 Clusters

Abstract

Due to distinctive quantum confinement effects, ultrasmall gold nanoparticles usually exhibit interesting electronic structure and molecular-like properties. However, lack of atom-precise structural information makes the understanding of them almost impossible such as to understand the relationships between their compositions and unique properties. Herein, by reducing a diphosphine AuI precursor (Au2(dppm)2Cl2, dppm = Ph2PCH2PPh2) with or without a S2- releasing reagent, we enriched our knowledge of the members in the families of Au13 and Au8 by the structural determinations of two new dppm-protected gold nanoclusters, [Au13(dppm)6]5+ (SD/Au1) and [Au8(dppm)4S2]2+ (SD/Au2), respectively. Within SD/Au1, the Au13 kernel significantly deviates from the ideal Ih icosahedron by the elongation of three surface Au-Au bonds to ~3.5 Å, giving it a C3 symmetry, whereas SD/Au2 has a novel heart-shaped C2 symmetric Au8S2 core (central Au4 tetrahedron + two Au2S units) protected by four μ2-dppm ligands in the outer shell. Of note, SD/Au1 represents a rare Au13 nanocluster with an opened icosahedral geometry, and SD/Au2 shows a new edge-shared “core + 4 exo” structure type that has never been observed ever before. The electronic structures and optical absorption spectra of these systems are correlated with time-dependent density functional theory (TDDFT) calculations. Based on the spherical Jellium model, the stability of Au13 and Au8 nanoclusters can be ascribed to 8- and 2-electron superatoms with 1S21P6 and 1S2 configurations, respectively. Interestingly, cluster SD/Au2 exhibits bright yellow luminescence with an emission maximum at 591 nm that slightly hypsochromically shifts to 581 nm upon cooling to 93 K. Our findings not only enrich the family of diphosphine-protected ultrasmall gold nanoclusters, but also demonstrate the rich variations of gold kernels during the transformation from simple AuI precursor to Au nanoclusters.

Back to tab navigation

Supplementary files

Publication details

The article was received on 15 Aug 2017, accepted on 03 Dec 2017 and first published on 04 Dec 2017


Article type: Edge Article
DOI: 10.1039/C7SC03566G
Citation: Chem. Sci., 2017, Accepted Manuscript
  • Open access: Creative Commons BY license
  •   Request permissions

    Diphosphine-Protected Ultrasmall Gold Nanoclusters: Opened Icosahedral Au13 and Heart-Shaped Au8 Clusters

    S. Zhang, L. Feng, R. Senanayake, C. M. Aikens, X. Wang, Q. Zhao, C. Tung and D. Sun, Chem. Sci., 2017, Accepted Manuscript , DOI: 10.1039/C7SC03566G

    This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. Material from this article can be used in other publications provided that the correct acknowledgement is given with the reproduced material.

    Reproduced material should be attributed as follows:

    • For reproduction of material from NJC:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the Centre National de la Recherche Scientifique (CNRS) and the RSC.
    • For reproduction of material from PCCP:
      [Original citation] - Published by the PCCP Owner Societies.
    • For reproduction of material from PPS:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the European Society for Photobiology, the European Photochemistry Association, and RSC.
    • For reproduction of material from all other RSC journals:
      [Original citation] - Published by The Royal Society of Chemistry.

    Information about reproducing material from RSC articles with different licences is available on our Permission Requests page.

Search articles by author

Spotlight

Advertisements