Through-Space Ultrafast Photoinduced Electron Transfer Dynamics of a C70-Encapsulated Bisporphyrin Covalent Organic Polyhedron in a Low-Dielectric Medium
Por:
Ortiz M., Cho S., Niklas J., Kim S., Poluektov O.G., Zhang W., Rumbles G., Park J.
Publicada:
1 ene 2017
Resumen:
Ultrafast photoinduced electron transfer (PIET) dynamics of a C70-encapsulated bisporphyrin covalent organic polyhedron hybrid (C70@COP-5) is studied in a nonpolar toluene medium with fluorescence and transient absorption spectroscopies. This structurally rigid donor (D)-acceptor (A) molecular hybrid offers a new platform featuring conformationally predetermined cofacial D-A orientation with a fixed edge-to-edge separation, REE (2.8 Å), without the aid of covalent bonds. Sub-picosecond PIET (tET = 0.4 ps) and very slow charge recombination (tCR ˜ 600 ps) dynamics are observed. The origin of these dynamics is discussed in terms of enhanced D-A coupling (V = 675 cm-1) and extremely small reorganization energy (? ˜ 0.18 eV), induced by the intrinsic structural rigidity of the C70@COP-5 complex. © 2017 American Chemical Society.
Filiaciones:
Ortiz M.:
Chemistry and Nanoscience Center, National Renewable Energy Laboratory, Golden, CO, United States
Department of Chemistry and Biochemistry, University of Colorado at Boulder, Boulder, CO, United States
Cho S.:
Department of Chemistry, Chonnam National University, Gwangju, South Korea
Niklas J.:
Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, IL, United States
Kim S.:
National Bioenergy Center, National Renewable Energy Laboratory, Golden, CO, United States
Poluektov O.G.:
Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, IL, United States
Zhang W.:
Department of Chemistry and Biochemistry, University of Colorado at Boulder, Boulder, CO, United States
Rumbles G.:
Chemistry and Nanoscience Center, National Renewable Energy Laboratory, Golden, CO, United States
Department of Chemistry and Biochemistry, University of Colorado at Boulder, Boulder, CO, United States
Renewable and Sustainable Energy Institute, University of Colorado at Boulder, Boulder, CO, United States
Park J.:
Chemistry and Nanoscience Center, National Renewable Energy Laboratory, Golden, CO, United States
Department of Molecular Engineering, Graduate School of Engineering, Kyoto University Nishikyo-ku, Kyoto, Japan
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