Reactivity of the charge transfer excited state of sodium decatungstate at the nanosecond time scale
Literature Information
J. A. Delaire, C. Giannotti
Previous studies have put into evidence the key role of a charge transfer excited state, noted X, in the primary steps of laser photolysis of sodium decatungstate solutions. In this work, we report a thorough study of the reactivity of the X transient towards different organic and inorganic substrates in acetonitrile and in water. The bimolecular reaction between X and the substrates is shown to occur on the nanosecond time-scale, either by H atom or electron transfer, and leads to the formation of the reduced form Y of decatungstate.We find that H atom transfer reactions are ruled by Z–H (Z=C, N, O) binding energies and lead to Y formation quantum yields that may reach the X formation quantum yield, whereas electron transfer reactions are ruled by the substrates' oxidation potential (Marcus reorganisation energy λ=1.0–1.3 eV for aromatics in acetonitrile) and lead to Y formation quantum yields similar to that obtained in the pure solvent.
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