EXPLORING THE PHOTOREDUCTION OF Au(III) COMPLEXES IN THE GAS-PHASE
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Date
2010
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Publisher
Ohio State University
Abstract
We have used photodissociation spectroscopy to probe the electronic structure and photoreduction of Au(III) in gas-phase complexes containing Cl$^{-}$ and OH$^{-}$. The gas-phase electronic spectrum of [AuCl$_4$]$^{-}$ closely resembles the aqueous solution spectrum, showing a lack of strong solvatochromic shifts. Substitution of Cl$^{-}$ ligands with OH$^{-}$ results in a strong blue shift, in agreement with ligand-field theory. Upon excitation, [AuCl$_4$]$^{-}$ can dissociate by loss of either one or two neutral Cl atoms, resulting in the reduction of gold from Au(III) to Au(II) and Au(I) respectively. The hydroxide substituted complex, [AuCl$_2$(OH)$_2$]$^{-}$, demonstrates similar behavior but the only observable fragment channel is the loss of two neutral OH ligands, leading only to Au(I).
Description
Author Institution: JILA, NIST, Department of Chemistry and Biochemistry, The University of Colorado, Boulder, CO