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Molecular-wire behaviour in p -phenylenevinylene oligomers

Nature volume 396, pages 60–63 (1998)Cite this article

Abstract

Electron transfer from electron-donor to electron-acceptor molecules via a molecular ‘bridge’ is a feature of many biological andchemical systems. The electronic structure of the bridge component in donor–bridge–acceptor (DBA) systems is known to play a critical role in determining the ease of electron transfer1,2. In most DBA systems, the rate at which electron transfer occurs scales exponentially with the donor–acceptor distance — effectively the length of the bridge molecule. But theory predicts that regimes exist wherein the distance dependence may be very weak, the bridge molecules essentially acting as incoherent molecular wires3,4,5,6. Here we show how these regimes can be accessed by molecular design. We have synthesized a series of structurally well-defined DBA molecules that incorporate tetracene as the donor and pyromellitimide as the acceptor, linked by p -phenylenevinylene oligomers of various lengths. Photoinduced electron transfer in this series exhibits very weak distance dependence for donor–acceptor separations as large as 40 Å, with rate constants of the order of 1011 s−1. These findings demonstrate the importance of energy matching between the donor and bridge components for achieving molecular-wire behaviour.

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Figure 1
Figure 2: Optical absorption spectra.
Figure 3: Distance dependence of charge separation and recombination rate constants.
Figure 4: The LUMO (solid lines) and HOMO (dashed lines) energies of TET and the five bridge molecules.

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Acknowledgements

This work was supported by the Division of Chemical Sciences, Office of Basic Energy Sciences, Department of Energy (M.R.W.), the Chemistry Division of the NSF and ONR (M.A.R.), and the Link Energy Foundation (W.B.D.).

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Authors and Affiliations

  1. Department of Chemistry, Northwestern University, Evanston, 60208-3113, Illinois, USA

    William B. Davis, Mark A. Ratner & Michael R. Wasielewski

  2. Chemistry Division, Argonne National Laboratory, Argonne, 60439-4831, Illinois, USA

    Walter A. Svec & Michael R. Wasielewski

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  1. William B. Davis
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Correspondence to Michael R. Wasielewski.

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Davis, W., Svec, W., Ratner, M. et al. Molecular-wire behaviour in p -phenylenevinylene oligomers. Nature 396, 60–63 (1998). https://doi.org/10.1038/23912

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