Pendant unit effect on electron tunneling in U-shaped molecules |
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Authors: | Min Liu Subhasis Chakrabarti David H Waldeck Anna M Oliver Michael N Paddon-Row |
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Institution: | 1. Chemistry Department, University of Pittsburgh, 219 Parkman Avenue, Pittsburgh, PA 15260, USA;2. School of Chemistry, University of New South Wales, Sydney NSW 2052, Australia |
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Abstract: | The electron transfer reactions of three U-shaped donor-bridge-acceptor molecules with different pendant groups have been studied in different solvents as a function of temperature. Analysis of the electron transfer kinetics in nonpolar and weakly polar solvents provides experimental reaction Gibbs energies that are used to parameterize a molecular solvation model. This solvation model is then used to predict energetic parameters in the electron transfer rate constant expression and allow the electronic coupling between the electron donor and electron acceptor groups to be determined from the rate data. The U-shaped molecules differ by alkylation of the aromatic pendant group, which lies in the ‘line-of-sight’ between the donor and acceptor groups. The findings show that the electronic coupling through the pendant group is similar for these molecules. |
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Keywords: | Electron transfer Electron tunneling Solvation |
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