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The atomic metal core structures of the subnanometer clusters Au13[PPh3]4[S(CH2)11CH3]2Cl2 (1) and Au13[PPh3]4[S(CH2)11CH3]4 (2) were characterized using advanced methods of electron microscopy and X-ray absorption spectroscopy. The number of gold atoms in the cores of these two clusters was determined quantitatively using high-angle annular dark field scanning transmission electron microscopy. Multiple-scattering-path analyses of extended X-ray absorption fine structure (EXAFS) spectra suggest that the Au metal cores of each of these complexes adopt an icosahedral structure with a relaxation of the icosahedral strain. Data from microscopy and spectroscopy studies extended to larger thiolate-protected gold clusters showing a broader distribution in nanoparticle core sizes (183 ± 116 Au atoms) reveal a bulklike fcc structure. These results further support a model for the monolayer-protected clusters (MPCs) in which the thiolate ligands bond preferentially at 3-fold atomic sites on the nanoparticle surface, establishing an average composition for the MPC of Au180[S(CH2)11CH3]40. Results from EXAFS measurements of a gold(I) dodecanethiolate polymer are presented that offer an alternative explanation for observations in previous reports that were interpreted as indicating Au MPC structures consisting of a Au core, Au2S shell, and thiolate monolayer.


Copyright 2006 American Chemical Society.

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Journal of Physical Chemistry B

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Menard, Laurent D.; Xu, Huiping; Gao, Shang-Peng; Twesten, Ray D.; Harper, Amanda S.; Song, Yang; Wang, Gangli; Douglas, Alicia D.; Yang, Judith C.; Frenkel, Anatoly I.; Murray, Royce W.; Nuzzo, Ralph G. “Metal Core Bonding Motifs of Monodisperse Icosahedral Au13 and Larger Au Monolayer-Protected Clusters As Revealed by X-ray Absorption Spectroscopy and Transmission Electron Microscopy.” Journal of Physical Chemistry B, 2006, 110 (30), 14564-14573.



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