Substituent effects on redox potentials and optical gap energies of molecule-like Au38(SPhX)24 nanoparticles

Rui Guo; Royce W Murray

doi:10.1021/ja053119m

Substituent effects on redox potentials and optical gap energies of molecule-like Au38(SPhX)24 nanoparticles

J Am Chem Soc. 2005 Aug 31;127(34):12140-3. doi: 10.1021/ja053119m.

Authors

Rui Guo¹, Royce W Murray

Affiliation

¹ Kenan Laboratories of Chemistry, University of North Carolina, Chapel Hill, North Carolina 27599-3290, USA.

PMID: 16117556
DOI: 10.1021/ja053119m

Abstract

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.