Photochemistry of iron(iiiit)-lactic acid complex in aqueous solutions

被引:18
|
作者
Pozdnyakov, I. P. [1 ,2 ]
Wu, F. [3 ]
Melnikov, A. A. [4 ]
Grivin, V. P. [3 ]
Bazhin, N. M. [1 ,2 ]
Chekalin, S. V. [4 ]
Plyusnin, V. F. [1 ,2 ]
机构
[1] Russian Acad Sci, Siberian Branch, Inst Chem Kinet & Combust, 3 Ul Inst Skaya, Novosibirsk 630090, Russia
[2] Novosibirsk State Univ, Novosibirsk 630090, Russia
[3] Wuhan Univ, Dept Environm Sci, Wuhan 430072, Hubei, Peoples R China
[4] Russian Acad Sci, Inst Spect, Moscow 142190, Russia
基金
俄罗斯基础研究基金会;
关键词
photochemistry; Fe(III) complexes; carboxylic acids; methyl viologen; laser flash photolysis; radical complexes; ULTRAFAST DECARBOXYLATION; PULSE-RADIOLYSIS; ACYLOXY RADICALS; PYRUVIC-ACID; IRON(III); DYNAMICS; FE(III); OXYGEN; PHOTODECOMPOSITION; FERRIOXALATE;
D O I
10.1007/s11172-013-0227-6
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Photochemistry of a 1: 1 Fe-III-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 [Fe-II...-O-CH(Me)-COO center dot](+) 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 [Fe-II...-O-CH(Me)-COO center dot](+) and its subsequent transformation to the end product of the photochemical reaction.
引用
收藏
页码:1579 / 1585
页数:7
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