Photochemistry of iron(iii)-lactic acid complex in aqueous solutions |
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Authors: | I P Pozdnyakov F Wu A A Melnikov V P Grivin N M Bazhin S V Chekalin V F Plyusnin |
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Institution: | 1. Institute of Chemical Kinetics and Combustion, Siberian Branch of the Russian Academy of Sciences, 3 ul. Institutskaya, 630090, Novosibirsk, Russian Federation 2. Novosibirsk State University, 3 ul. Pirogova, 630090, Novosibirsk, Russian Federation 3. Department of Environmental Science, Wuhan University, Wuhan, Hubei, P. R. China, 430072 4. Institute of Spectroscopy, Russian Academy of Sciences, 5 ul. Fizicheskaya, 142190, Troitsk, Moscow, Russian Federation
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Abstract: | Photochemistry of a 1: 1 FeIII-lactic acid complex, Fe(Lact)]+, in aqueous solutions was studied by stationary photolysis, nanosecond laser flash photolysis (355 nm, 6 ns), and femtosecond pump-probe spectroscopy (400 nm, 200 fs). The quantum yield of photolysis of Fe(Lact)]+ upon excitation at 355 nm is 0.4 and 0.22 in the deoxygenated and air-saturated solutions, respectively. Weak transient absorption in the range 500–750 nm was observed in the nanosecond experiments. It was assigned to a FeII...-O-CH(Me)-COO·]+ radical complex. The spectral properties of the ligand-to-metal charge transfer excited state and the characteristic time of formation of the radical complex (1.5 ps) were determined in the femtosecond spectroscopy experiments. A reaction mechanism was proposed, which involves inner-sphere electron transfer in the excited complex with the formation of a radical complex FeII...-O-CH(Me)-COO·]+ and its subsequent transformation to the end product of the photochemical reaction. |
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