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Ultrafast Electronic Energy Transfer Beyond the Weak Coupling Limit in a Proximal but Orthogonal Molecular Dyad

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Download Hi-Res ImageDownload to MS-PowerPointCite This:J. Phys. Chem. A 2015, 119, 51, 12665-12671
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    Ultrafast Electronic Energy Transfer Beyond the Weak Coupling Limit in a Proximal but Orthogonal Molecular Dyad
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    Organic Semiconductor Centre, SUPA, School of Physics and Astronomy, University of St Andrews, North Haugh, St Andrews, Fife, KY16 9SS, U.K.
    § Molecular Photonics Laboratory, School of Chemistry, Bedson Building, Newcastle University, Newcastle upon Tyne, NE1 7RU, U.K.
    *(A.H.) E-mail: [email protected]. Telephone: +44 191 2088660.
    *(I.D.W.S.) E-mail: [email protected]
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    The Journal of Physical Chemistry A

    Cite this: J. Phys. Chem. A 2015, 119, 51, 12665–12671
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    https://doi.org/10.1021/acs.jpca.5b08640
    Published November 28, 2015
    Copyright © 2015 American Chemical Society
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    Abstract

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    Electronic energy transfer (EET) from a donor to an acceptor is an important mechanism that controls the light harvesting efficiency in a wide variety of systems, including artificial and natural photosynthesis and contemporary photovoltaic technologies. The detailed mechanism of EET at short distances or large angles between the donor and acceptor is poorly understood. Here the influence of the orientation between the donor and acceptor on EET is explored using a molecule with two nearly perpendicular chromophores. Very fast EET with a time constant of 120 fs is observed, which is at least 40 times faster than the time predicted by Coulombic coupling calculations. Depolarization of the emission signal indicates that the transition dipole rotates through ca. 64°, indicating the near orthogonal nature of the EET event. The rate of EET is found to be similar to structural relaxation rates in the photoexcited oligothiophene donor alone, which suggests that this initial relaxation brings the dyad to a conical intersection where the excitation jumps to the acceptor.

    Copyright © 2015 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jpca.5b08640.

    • Autoreconvolution data, depolarization fitting, anisotropy of BODIPY, formulas of control compounds, energy-minimized geometries, comparison of absorption/excitation spectra, and Kohn–Sham representations, fluorescence spectra after excitation into oligothiophene at 77 K and room temperature (PDF)

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    Cited By

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    This article is cited by 22 publications.

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    The Journal of Physical Chemistry A

    Cite this: J. Phys. Chem. A 2015, 119, 51, 12665–12671
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.jpca.5b08640
    Published November 28, 2015
    Copyright © 2015 American Chemical Society
    Request reuse permissions

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