pH Dependence of Photoinduced Electron Transfer with [Ru(TAP)3]2+
(2017) Inorganic Chemistry — Vol. 56, n° 4, p. 1794-1803 (2017)
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- Abstract
- The quenching of the excited state of [Ru(TAP)3]2+ (TAP = 1,4,5,8-tetraazaphenanthrene) by guanosine-5′-monophosphate (GMP), N-acetyltyrosine (N-Ac-Tyr), and hydroquinone (H2Q) has been studied in aqueous solution over a wide range of pH values including, for the first time, strongly acidic media. This quenching by electron transfer was examined by steady-state 1H photochemically induced dynamic nuclear polarization (photo-CIDNP) as well as by more conventional techniques, among which are pulsed laser-induced transient absorption and emission experiments. A deeper knowledge of the photochemical behavior of [Ru(TAP)3]2+ has been gained thanks to the combined use of these two approaches, photo-CIDNP and electronic spectroscopies, highlighting their complementarity. In contrast to what was believed, it is found that the protonated excited state of [Ru(TAP)3]2+ may give rise to an electron transfer with N-Ac-Tyr and H2Q. Such a photoinduced electron transfer does not occur with protonated GMP, however. 1H photo-CIDNP experiments are expected to be particularly promising for characterization of the reductive quenching of excited-state ruthenium(II) polypyridyl complexes comprising several nonequivalent protonation sites.
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Troian-Gautier, L., Mugeniwabagara, E., Fusaro, L., Moucheron, C., Kirsch-De Mesmaeker, A., & Luhmer, M. (2017). pH Dependence of Photoinduced Electron Transfer with [Ru(TAP)3]2+. Inorganic Chemistry, 56(4), 1794-1803. https://doi.org/10.1021/acs.inorgchem.6b01780 (Original work published 2017)