1. Bambusuril as a One-Electron Donor for Photoinduced Electron Transfer to Methyl Viologen in Mixed Crystals
- Author
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Lucie Ludvíková, Marek Nečas, Petr Kulhánek, Petr Klán, Dominik Heger, Vladimir Sindelar, Jan Švec, L’ubica Vetráková, Tomas Fiala, Tomáš Slanina, and Michal Babiak
- Subjects
chemistry.chemical_classification ,010405 organic chemistry ,Chemistry ,Viologen ,Electron donor ,General Chemistry ,Crystal structure ,010402 general chemistry ,Photochemistry ,01 natural sciences ,Biochemistry ,Catalysis ,Photoinduced electron transfer ,0104 chemical sciences ,chemistry.chemical_compound ,Colloid and Surface Chemistry ,Hexafluorophosphate ,medicine ,Cyclic voltammetry ,Counterion ,Acetonitrile ,medicine.drug - Abstract
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.
- Published
- 2017