Bambusuril as a One-Electron Donor for Photoinduced Electron Transfer to Methyl Viologen in Mixed Crystals

Methyl viologen hexafluorophosphate (MV2+·2PF6 –) and dodecamethylbambus[6]­uril (BU6) form crystals in which the layers of viologen dications alternate with those of a 1:2 supramolecular complex of BU6 and PF6 –. This arrangement allows for a one-electron reduction of MV2+ ions upon UV irradiation...

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Published in:Journal of the American Chemical Society 2017-02, Vol.139 (7), p.2597-2603
Main Authors: Fiala, Tomas, Ludvíková, Lucie, Heger, Dominik, Švec, Jan, Slanina, Tomáš, Vetráková, L’ubica, Babiak, Michal, Nečas, Marek, Kulhánek, Petr, Klán, Petr, Sindelar, Vladimir
Format: Article
Language:English
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Summary:Methyl viologen hexafluorophosphate (MV2+·2PF6 –) and dodecamethylbambus[6]­uril (BU6) form crystals in which the layers of viologen dications alternate with those of a 1:2 supramolecular complex of BU6 and PF6 –. This arrangement allows for a one-electron reduction of MV2+ ions upon UV irradiation to form MV+• radical cations within the crystal structure with half-lives of several hours in air. The mechanism of this photoinduced electron transfer in the solid state and the origin of the long-lived charge-separated state were studied by steady-state and transient spectroscopies, cyclic voltammetry, and electron paramagnetic resonance spectroscopy. Our experiments are supported by quantum-chemical calculations showing that BU6 acts as a reductant. In addition, analogous photochemical behavior is also demonstrated on other MV2+/BU6 crystals containing either BF4 – or Br– counterions.
ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.6b08589