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

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Publikace nespadá pod Ekonomicko-správní fakultu, ale pod Přírodovědeckou fakultu. Oficiální stránka publikace je na webu muni.cz.
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FIALA Tomáš LUDVÍKOVÁ Lucie HEGER Dominik ŠVEC Jan SLANINA Tomáš VETRÁKOVÁ Ľubica BABIAK Michal NEČAS Marek KULHÁNEK Petr KLÁN Petr ŠINDELÁŘ Vladimír

Rok publikování 2017
Druh Článek v odborném periodiku
Časopis / Zdroj Journal of the American Chemical Society
Fakulta / Pracoviště MU

Přírodovědecká fakulta

Citace
www http://pubs.acs.org/doi/10.1021/jacs.6b08589
Doi http://dx.doi.org/10.1021/jacs.6b08589
Obor Organická chemie
Klíčová slova DENSITY-FUNCTIONAL CALCULATIONS; ORDER REGULAR APPROXIMATION; CHARGE-TRANSFER SALTS; MOLECULAR-DYNAMICS; CATION RADICALS; METHYLVIOLOGEN; REDUCTION; PHOTOCHEMISTRY; ORGANOSILICA; ACETONITRILE
Popis Methyl viologen hexafluorophosphate (MV2+center dot 2PF(6)(-)) 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+center dot 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.
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