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Inorganics 2017, 5(2), 21;

Photophysics of BODIPY Dyes as Readily-Designable Photosensitisers in Light-Driven Proton Reduction

Leibniz-Institut für Katalyse e.V. an der Universität Rostock, Albert-Einstein-Str. 29a, 18057 Rostock, Germany
Leibniz-Institut für Photonische Technologien e.V. Jena, Albert-Einstein-Straße 9, 07745 Jena, Germany
Friedrich-Schiller-Universität Jena, Institut für Physikalische Chemie und, Helmholtzweg 4, 07743 Jena, Germany
Institut für Anorganische und Analytische Chemie, TU Braunschweig, Hagenring 30, 38106 Braunschweig, Germany
Current address: Institut Catatà d´Investigació Química, Avinguda dels Països Catalans 16, 43007 Tarragona, Spain
Current address: Department of Chemistry and Molecular Biology, University of Gothenburg, 40530 Gothenburg, Sweden
Authors to whom correspondence should be addressed.
Academic Editor: Matthias Bauer
Received: 27 February 2017 / Revised: 28 March 2017 / Accepted: 29 March 2017 / Published: 5 April 2017
(This article belongs to the Special Issue Photochemical Water Splitting)
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A series of boron dipyrromethene (BODIPY) dyes was tested as photosensitisers for light-driven hydrogen evolution in combination with the complex [Pd(PPh3)Cl2]2 as a source for catalytically-active Pd nanoparticles and triethylamine as a sacrificial electron donor. In line with earlier reports, halogenated dyes showed significantly higher hydrogen production activity. All BODIPYs were fully characterised using stationary absorption and emission spectroscopy. Time-resolved spectroscopic investigations on meso-mesityl substituted compounds revealed that reduction of the photo-excited BODIPY by the sacrificial agent occurs from an excited singlet state, while, in halogenated species, long-lived triplet states are present, determining electron transfer processes from the sacrificial agent. Quantum chemical calculations performed at the time-dependent density functional level of theory indicate that the differences in the photocatalytic performance of the present series of dyes can be correlated to the varying efficiency of intersystem crossing in non-halogenated and halogenated species and not to alterations in the energy levels introduced upon substitution. View Full-Text
Keywords: BODIPY; hydrogen; photochemistry; photophysics; quantum chemical simulations BODIPY; hydrogen; photochemistry; photophysics; quantum chemical simulations

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Dura, L.; Wächtler, M.; Kupfer, S.; Kübel, J.; Ahrens, J.; Höfler, S.; Bröring, M.; Dietzek, B.; Beweries, T. Photophysics of BODIPY Dyes as Readily-Designable Photosensitisers in Light-Driven Proton Reduction. Inorganics 2017, 5, 21.

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