Studying and Switching Electron Transfer:  From the Ensemble to the Single Molecule

We report here on the systematic investigation of photoinduced intramolecular electron transfer (IET) in a series of donor−bridge−acceptor molecules as a means of understanding electron transport through the bridge. Perylenebisimide chromophores connected by various oligophenylene bridges are studie...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2004-12, Vol.126 (49), p.16126-16133
Main Authors: Holman, Michael W, Liu, Ruchuan, Zang, Ling, Yan, Ping, DiBenedetto, Sara A, Bowers, Robert D, Adams, David M
Format: Article
Language:English
Subjects:
Atomic and molecular collision processes and interactions
Atomic and molecular physics
Exact sciences and technology
Fluorescence and phosphorescence
radiationless transitions, quenching (intersystem crossing, internal conversion)
Intramolecular energy transfer
intramolecular dynamics
dynamics of van der waals molecules
Molecular properties and interactions with photons
Physics
Radiationless transitions, quenching
Rotational and vibrational energy transfer
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Summary:We report here on the systematic investigation of photoinduced intramolecular electron transfer (IET) in a series of donor−bridge−acceptor molecules as a means of understanding electron transport through the bridge. Perylenebisimide chromophores connected by various oligophenylene bridges are studied because their electron-transfer behavior can readily be monitored by following changes in the fluorescence intensity. We find dramatic switching of the IET behavior as the solvent polarity (dielectric constant) is increased. By combining steady-state and time-resolved fluorescence spectroscopy in a variety of solvents at multiple temperatures with standard theories of electron transfer, we determine parameters governing the IET behavior of these dimers, such as the electronic coupling through the bridges. We also deploy available ab initio quantum chemical methods to calculate the through-space component of the electronic coupling matrix element. Single-molecule investigations of the electron-transfer behavior also show that IET can be switched reversibly by a similar mechanism in an isolated individual molecule.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja047386o