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Article

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

Supporting Info

Rui Guo and Royce W. Murray*

Contribution from the Kenan Laboratories of Chemistry, University of North Carolina, Chapel Hill, North Carolina 27599-3290

J. Am. Chem. Soc., 2005, 127 (34), pp 12140–12143

DOI: 10.1021/ja053119m

Publication Date (Web): August 6, 2005

In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

, rwm@email.unc.edu

Abstract

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.

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Published In Issue August 31, 2005
Received May 12, 2005

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Article

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