Bambusuril as a One-Electron Donor for Photoinduced Electron Transfer to Methyl Viologen in Mixed Crystals
| Authors | |
|---|---|
| Year of publication | 2017 |
| Type | Article in Periodical |
| Magazine / Source | Journal of the American Chemical Society |
| MU Faculty or unit | |
| Citation | |
| Web | http://pubs.acs.org/doi/10.1021/jacs.6b08589 |
| Doi | http://dx.doi.org/10.1021/jacs.6b08589 |
| Field | Organic chemistry |
| Keywords | DENSITY-FUNCTIONAL CALCULATIONS; ORDER REGULAR APPROXIMATION; CHARGE-TRANSFER SALTS; MOLECULAR-DYNAMICS; CATION RADICALS; METHYLVIOLOGEN; REDUCTION; PHOTOCHEMISTRY; ORGANOSILICA; ACETONITRILE |
| Description | 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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