Abstract
A series of ..cap alpha..-diimine Ru(II) sensitizers were studied in aqueous, alcohol, and sodium lauryl sulfate (NaLS) micellar solutions. The emission efficiency, lifetime, and spectra change dramatically on micellization. From the temperature dependence of the excited-state lifetime and luminescence quantum efficiencies, coupled with spectral fitting, they interpret these changes and elucidate the environment of the micellized sensitizer. The increased efficiencies and lifetimes on micellization arise from decreased rates of deactivation via the photoactive d-d state and by a decrease in other intramolecular nonradiative paths. Radiationless decay theory permits semiquantitative calculation of nonradiative rate constants. A model describing the binding site and local solvent environment for the sensitizers is proposed. Implications of the results for solar energy conversion schemes are described.
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