Title

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

Authors

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

Document Type

Article

Article Version

Publisher's PDF

Publication Date

2006

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.

Comments

Copyright 2006 American Chemical Society

The published article is also available on the journal site:

http://pubs.acs.org/doi/abs/10.1021/jp060739g

Publication Title

Journal of Physical Chemistry B

Repository Citation

Menard, Laurent D.; Gao, Shang-Peng; Xu, Huiping; Twesten, Ray D.; Harper-Leatherman, Amanda S.; Song, Yang; Wang, Gangli; Douglas, Alicia D.; Yang, Judith C.; Frenkel, Anatoly I.; Nuzzo, Ralph G.; and Murray, Royce W., "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" (2006). Chemistry & Biochemistry Faculty Publications. 6.
https://digitalcommons.fairfield.edu/chemistry-facultypubs/6

Published Citation

Menard , Laurent D.; Gao, Sheng-Peng; Xu, Huiping; Twesten, Ray D.; Harper, Amanda S.; Song, Yang; Wang, Gangli; Douglas, Alicia D.; Yang, Judith C.; Frenkel, Anatoly I.; Nuzzo, Ralph G.; Murray, Royce W. “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.” Journal of Physical Chemistry B, 2006, 110 (26), 12874-12883.

DOI

10.1021/jp060739g

Peer Reviewed