Substituent Effects on Redox Potentials and Optical Gap Energies of Molecule-like Au38(SPhX)24 Nanoparticles

A molecule-like substituent effect on redox formal potentials in the nanoparticle series Au38(SPhX)24 has been discovered. Electron-withdrawing “X” substituents energetically favor reduction and disfavor oxidation, and give formal potentials that correlate with Hammett substituent constants. The lig...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2005-08, Vol.127 (34), p.12140-12143
Main Authors: Guo, Rui, Murray, Royce W
Format: Article
Language:English
Subjects:
Atomic and molecular clusters
Atomic and molecular physics
Electronic and magnetic properties of clusters
Exact sciences and technology
Physics
Studies of special atoms, molecules and their ions
clusters
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Summary:A molecule-like substituent effect on redox formal potentials in the nanoparticle series Au38(SPhX)24 has been discovered. Electron-withdrawing “X” substituents energetically favor reduction and disfavor oxidation, and give formal potentials that correlate with Hammett substituent constants. The ligand monolayer of the nanoparticles is shown, thereby, to play a strong role in determining electronic energies of the nanoparticle core and is more than simply a protecting or capping layer. The substituent effect does not, however, detectably change the HOMO−LUMO gap energy, being identical for the HOMO and LUMO levels and presumably inductive in nature.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja053119m