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The relaxation dynamics and product distribution resulting from the decay of high lying excited states generated via sequential two-photon capture by [Ru(bpy) 3 ] 2+ or electron capture by [Ru(bpy) 3 ] 3+ have been investigated by flash photolysis and pulse radiolysis techniques. In comparison to the decay dynamics for monophotonic excitation, dramatically different relaxation dynamics have been observed. High-power flash excitation yields both the lowest lying metal-to-ligand charge transfer ( 3 MLCT) state and a new transient photoproduct associated with nonradiative decay through the photodissociative metal-centered ( 3 dd) excited state/s. The photoproduct is postulated to be [Ru II (bpy) 2 ( η 1 -bpy)] 2+ where the pendant pyridine has rotated to yield a transient that is stabilized by a π−bonded or a three-centered Ru−C−H agostic interaction.
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Thompson et al. (2001) studied this question.
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