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Light Harvesting and Charge Separation in a π-Conjugated Antenna Polymer Bound to TiO2

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    Light Harvesting and Charge Separation in a π-Conjugated Antenna Polymer Bound to TiO2
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    † Department of Chemistry, University of Florida, Gainesville, Florida 32611, United States
    ‡ Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599, United States
    § School of Chemistry and Biochemistry, School of Materials Science and Engineering, Center for Organic Photonics and Electronics, Georgia Institute of Technology, Atlanta, Georgia 30332, United States
    *E-mail [email protected] (K.S.S.).
    *E-mail [email protected] (J.M.P.).
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    The Journal of Physical Chemistry C

    Cite this: J. Phys. Chem. C 2014, 118, 49, 28535–28541
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    https://doi.org/10.1021/jp5113558
    Published November 17, 2014
    Copyright © 2014 American Chemical Society
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    Abstract

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    This paper describes the photophysical and photoelectrochemical characterization of a light harvesting polychromophore array featuring a polyfluorene backbone with covalently attached Ru(II) polypyridyl complexes (PF-Ru-A), adsorbed on the surface of mesostructured TiO2 (PF-Ru-A//TiO2). The surface adsorbed polymer is characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), and attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy, providing evidence for the morphology of the surface adsorbed polymer and the mode of binding. Photoexcitation of the Ru(II) complexes bound to the metal oxide surface (proximal) results in electron injection into the conduction band of TiO2, which is then followed by ultrafast hole transfer to the polymer to form oxidized polyfluorene (PF+). More interestingly, chromophores that are not directly bound to the TiO2 interface (distal) that are excited participate in site-to-site energy transfer processes that transport the excited state to surface bound chromophores where charge injection occurs, underscoring the antenna-like nature of the polymer assembly. The charge separated state is long-lived and persists for >100 μs, a consequence of the increased separation between the hole and injected electron.

    Copyright © 2014 American Chemical Society

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    Supporting Information

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    Experimental procedures, ATR-FTIR, TEM, AFM, J–V curve, absorption and emission spectra of PF-Ru-A//TiO2 films, and transient absorption spectra of PF-Ru-A//ZrO2 results. This material is available free of charge via the Internet at http://pubs.acs.org.

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    Cite this: J. Phys. Chem. C 2014, 118, 49, 28535–28541
    Click to copy citationCitation copied!
    https://doi.org/10.1021/jp5113558
    Published November 17, 2014
    Copyright © 2014 American Chemical Society
    Request reuse permissions

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