Issue 12, 2014

Photoinduced electron transfer across molecular bridges: electron- and hole-transfer superexchange pathways

Abstract

Photoinduced electron transfer plays key roles in many areas of chemistry. Superexchange is an effective model to rationalize photoinduced electron transfer, particularly when molecular bridges between donor and acceptor subunits are present. In this tutorial review we discuss, within a superexchange framework, the complex role played by the bridge, with an emphasis on differences between thermal and photoinduced electron transfer, oxidative and reductive photoinduced processes, charge separation and charge recombination. Modular bridges are also considered, with specific attention to the distance dependence of donor–acceptor electronic coupling and electron transfer rate constants. The possibility of transition, depending on the bridge energetics, from coherent donor–acceptor electron transfer to incoherent charge injection and hopping through the bridge is also discussed. Finally, conceptual analogies between bridge effects in photoinduced electron transfer and optical intervalence transfer are outlined. Selected experimental examples, instrumental to illustration of the principles, are discussed.

Graphical abstract: Photoinduced electron transfer across molecular bridges: electron- and hole-transfer superexchange pathways

Article information

Article type
Tutorial Review
Submitted
17 dec 2013
First published
06 mar 2014

Chem. Soc. Rev., 2014,43, 4005-4018

Author version available

Photoinduced electron transfer across molecular bridges: electron- and hole-transfer superexchange pathways

M. Natali, S. Campagna and F. Scandola, Chem. Soc. Rev., 2014, 43, 4005 DOI: 10.1039/C3CS60463B

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