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Menard LD, Gao SP, Xu H, et al. Sub-nanometer Au monolayer-protected clusters exhibiting molecule-like electronic behavior: quantitative high-angle annular dark-field scanning transmission electron microscopy and electrochemical characterization of clusters with precise atomic stoichiometry. J Phys Chem B. 2006;110(26):12874-83doi: 10.1021/jp060739g.
Menard, L. D., Gao, S. P., Xu, H., Twesten, R. D., Harper, A. S., Song, Y., Wang, G., Douglas, A. D., Yang, J. C., Frenkel, A. I., Nuzzo, R. G., & Murray, R. W. (2006). Sub-nanometer Au monolayer-protected clusters exhibiting molecule-like electronic behavior: quantitative high-angle annular dark-field scanning transmission electron microscopy and electrochemical characterization of clusters with precise atomic stoichiometry. The journal of physical chemistry. B, 110(26), 12874-83. https://doi.org/10.1021/jp060739g
Menard, Laurent D, et al. "Sub-nanometer Au monolayer-protected clusters exhibiting molecule-like electronic behavior: quantitative high-angle annular dark-field scanning transmission electron microscopy and electrochemical characterization of clusters with precise atomic stoichiometry." The journal of physical chemistry. B vol. 110,26 (2006): 12874-83. doi: https://doi.org/10.1021/jp060739g
Menard LD, Gao SP, Xu H, Twesten RD, Harper AS, Song Y, Wang G, Douglas AD, Yang JC, Frenkel AI, Nuzzo RG, Murray RW. Sub-nanometer Au monolayer-protected clusters exhibiting molecule-like electronic behavior: quantitative high-angle annular dark-field scanning transmission electron microscopy and electrochemical characterization of clusters with precise atomic stoichiometry. J Phys Chem B. 2006 Jul 06;110(26):12874-83. doi: 10.1021/jp060739g. PMID: 16805585.
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J Phys Chem B. 2006 Jul 06;110(26):12874-83. doi: 10.1021/jp060739g.

Sub-nanometer Au monolayer-protected clusters exhibiting molecule-like electronic behavior: quantitative high-angle annular dark-field scanning transmission electron microscopy and electrochemical characterization of clusters with precise atomic stoichiometry.

The journal of physical chemistry. B

Laurent D Menard, Shang-Peng Gao, Huiping Xu, Ray D Twesten, Amanda S Harper, Yang Song, Gangli Wang, Alicia D Douglas, Judith C Yang, Anatoly I Frenkel, Ralph G Nuzzo, Royce W Murray

Affiliations

  1. School of Chemical Sciences and Frederick Seitz Materials Research Laboratory, University of Illinois at Urbana-Champaign, Urbana, Illinois, 61801, USA.

PMID: 16805585 DOI: 10.1021/jp060739g

Abstract

The synthesis and characterization of the clusters Au13[PPh3]4[S(CH2)11CH3]2Cl2 (1) and Au13[PPh3]4[S(CH2)11CH3]4 (2) are described. These mixed-ligand, sub-nanometer clusters, prepared via exchange of dodecanethiol onto phosphine-halide gold clusters, show enhanced stability relative to the parent. The characterization of these clusters features the precise determination of the number of gold atoms in the cluster cores using high-angle annular dark-field scanning transmission electron microscopy, allowing the assignment of 13 gold atoms (+/-3 atoms) to the composition of both cluster molecules. Electrochemical and optical measurements reveal discrete molecular orbital levels and apparent energy gaps of 1.6-1.7 eV for the two cluster molecules. The electrochemical measurements further indicate that the Au13[PPh3]4[S(CH2)11CH3]2Cl2 cluster undergoes an overall two-electron reduction. The electrochemical and spectroscopic properties of the two Au13 cluster molecules are compared with those of a secondary synthetic product, which proved to be larger Au thiolate-derivatized monolayer-protected clusters with an average core of Au180. The latter shows behavior fully consistent with the adoption of metallic-like properties.

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