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  • Review Article
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The gold–sulfur interface at the nanoscale

Nature Chemistry volume 4, pages 443–455 (2012)Cite this article

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Abstract

Thiolate-protected gold surfaces and interfaces, relevant for self-assembled monolayers of organic molecules on gold, for passivated gold nanoclusters and for molecule–gold junctions, are archetypal systems in various fields of current nanoscience research, materials science, inorganic chemistry and surface science. Understanding this interface at the nanometre scale is essential for a wide range of potential applications for site-specific bioconjugate labelling and sensing, drug delivery and medical therapy, functionalization of gold surfaces for sensing, molecular recognition and molecular electronics, and gold nanoparticle catalysis. During the past five years, considerable experimental and theoretical advances have furthered our understanding of the molecular structure of the gold–sulfur interface in these systems. This Review discusses the recent progress from the viewpoint of theory and computations, with connections to relevant experiments.

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Figure 1: Schematics of bonding motifs between thiolates and gold.
Figure 2: Computed structures, bonding motifs and electronic states of gold–thiolate complexes.
Figure 3: STM images and atomistic interpretation of the structure of the low-coverage striped phase of methylthiolates CH3S on Au(111).
Figure 4: DFT-optimized atomistic models for the saturation-coverage c(4 × 2) methylthiolate–gold interface and photoemission core-level shifts.
Figure 5: Analysis of the single-crystal X-ray structure of para-mercaptobenzoic acid (p-MBA) protected cluster, Au102(p-MBA)44.
Figure 6: Structures of the Au25(SR)18− and Au144(SR)60 clusters.
Figure 7: Chiral recognition and response of organosulfur molecules at various gold surfaces.
Figure 8: Schematics of Au–BDT–Au junctions and computed structures, conductance and dynamics by using the novel RS(AuSR)n motif.

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Acknowledgements

I am indebted to collaborators and co-authors of refs. 35, 38, 56, 75, 77, 78, 79, 80, 81, 82, 99, 121, 125, 126 and 131, and I thank C. J. Ackerson for useful comments on the manuscript. This work has long-standing support from the Academy of Finland and the CSC—the Finnish IT Center for Science.

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  1. Departments of Physics and Chemistry, Nanoscience Center, University of Jyväskylä, Jyväskylä, FI-40014, Finland

    Hannu Häkkinen

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Häkkinen, H. The gold–sulfur interface at the nanoscale. Nature Chem 4, 443–455 (2012). https://doi.org/10.1038/nchem.1352

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