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Through-Bond Electronic Couplings in Intramolecular Electron Transfer Reactions

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Supramolecular Photochemistry

Part of the book series: NATO ASI Series ((ASIC,volume 214))

Abstract

Electron transfer is studied in molecules of the structure DBA where D and A (the donor and acceptor) are π systems and B is a saturated hydrocarbon bridge. Pulse radiolysis is used to produce radical anions of such molecules. In some ions, electron transfer rates can be measured, while in others the rates are too fast for measurement, but optical electron transfer (intervalence) bands can be observed. Both the rates and the band intensities decrease rapidly with increasing distance. Electronic couplings of the D and A groups occur through the saturated bonds of the bridge. The couplings are compared to couplings measured in related molecules by photoelectron and electron transmission spectroscopies. The dependence of the couplings on nuclear coordinates is discussed.

Work performed under the auspices of the Office of Basic Energy Sciences, Division of Chemical Science, US-DOE under contract number W-31-109-ENG-38.

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Authors and Affiliations

  1. Chemistry Division, Argonne National Laboratory, 60439, Argonne, IL, USA

    J. R. Miller

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Editors and Affiliations

  1. Department of Chemistry “G. Ciamician”, University of Bologna and Institute of FRAE-CNR, Bologna, Italy

    Vincenzo Balzani

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© 1987 D. Reidel Publishing Company

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Miller, J.R. (1987). Through-Bond Electronic Couplings in Intramolecular Electron Transfer Reactions. In: Balzani, V. (eds) Supramolecular Photochemistry. NATO ASI Series, vol 214. Springer, Dordrecht. https://doi.org/10.1007/978-94-009-3979-0_15

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  • DOI: https://doi.org/10.1007/978-94-009-3979-0_15

  • Publisher Name: Springer, Dordrecht

  • Print ISBN: 978-94-010-8265-5

  • Online ISBN: 978-94-009-3979-0

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