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Electron transfer through rigid organic molecular wires enhanced by electronic and electron–vibration coupling

Nature Chemistry volume 6, pages 899–905 (2014)Cite this article

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Abstract

Electron transfer (ET) is a fundamental process in a wide range of biological systems, photovoltaics and molecular electronics. Therefore to understand the relationship between molecular structure and ET properties is of prime importance. For this purpose, photoinduced ET has been studied extensively using donor–bridge–acceptor molecules, in which π-conjugated molecular wires are employed as bridges. Here, we demonstrate that carbon-bridged oligo-p-phenylenevinylene (COPV), which is both rigid and flat, shows an 840-fold increase in the ET rate compared with the equivalent flexible molecular bridges. A 120-fold rate enhancement is explained in terms of enhanced electronic coupling between the electron donor and the electron acceptor because of effective conjugation through the COPVs. The remainder of the rate enhancement is explained by inelastic electron tunnelling through COPV caused by electron–vibration coupling, unprecedented for organic molecular wires in solution at room temperature. This type of nonlinear effect demonstrates the versatility and potential practical utility of COPVs in molecular device applications.

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Figure 1: Structures of compounds used in this study.
Figure 2: Steady-state spectra and femtosecond flash photolysis in THF at room temperature.
Figure 3: Charge-separated state energies for ZnP•+–COPVn–C60•− and ZnP–COPVn•+–C60•− (n = 1–4) in anisole, THF and benzonitrile.
Figure 4: Arrhenius analyses of CS and CR in argon-saturated benzonitrile.
Figure 5: ET reaction mechanism.

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Acknowledgements

This work was supported by a Specially Promoted Research Grant (KAKENHI 22000008 to E.N.) and by JST-PRESTO ‘New Materials Science and Element Strategy’ (for H.T.). This work was supported by Deutsche Forschungsgemeinschaft as part of the Excellence Cluster ‘Engineering of Advanced Materials’. We thank R. D. Costa for calculations and valuable comments.

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Authors and Affiliations

  1. Department of Chemistry, School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-0033, Japan

    Junpei Sukegawa, Xiaozhang Zhu, Hayato Tsuji & Eiichi Nakamura

  2. Department of Chemistry and Pharmacy and Interdisciplinary Center for Molecular Materials, Friedrich-Alexander-Universität Erlangen-Nürnberg, Erlangen, 91058, Germany

    Christina Schubert & Dirk M. Guldi

  3. JST-PRESTO, 4-1-8 Honcho, Kawaguchi, 332-0012, Saitama, Japan

    Hayato Tsuji

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  1. Junpei Sukegawa
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Contributions

J.S. carried out molecular design, synthesis and data analysis, X.Z. carried out synthesis, H.T. and E.N. provided the system design and data analysis, C.S. carried out spectral data collection and analysis, and D.M.G. designed the spectral experiments and data analysis. All authors contributed equally to the preparation of the manuscript.

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Correspondence to Hayato Tsuji, Dirk M. Guldi or Eiichi Nakamura.

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Sukegawa, J., Schubert, C., Zhu, X. et al. Electron transfer through rigid organic molecular wires enhanced by electronic and electron–vibration coupling. Nature Chem 6, 899–905 (2014). https://doi.org/10.1038/nchem.2026

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