Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 127, Issue 34, Pages 12140-12143Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ja053119m
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A molecule-like substituent effect on redox formal potentials in the nanoparticle series Au-38(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.
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