Journal
JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY
Volume 268, Issue -, Pages 24-36Publisher
ELSEVIER SCIENCE SA
DOI: 10.1016/j.jphotochem.2013.06.022
Keywords
Iron; Carboxylate; Complex; Photochemistry; Quantum yield
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Fe(III) carboxylato complex photochemistry can be of interest for environmental aqueous systems, oxidative processing of wastewater or laboratory photochemical applications in general. A comprehensive dataset of Fe2+ quantum yields from the photolysis of aqueous Fe(III) complexes with malonate, succinate, glutarate, DL-tartrate, tartronate, gluconate, DL-lactate, DL-malate, pyruvate and glyoxalate has been measured. Irradiation techniques included single laser flash photolysis at 308 and 351 nm and continuous photolysis with a Hg(Xe) lamp-monochromator system at 313, 366, 405 and 436 nm. Complexes with ligands having a higher oxygen to carbon ratio tend to exhibit better photoreduction ability. Ligands containing OH, keto or diol functional groups in the a-position exhibit higher quantum yields than unsubstituted carboxylates (R-CH2-COOH). Generally, dissolved O-2 lowers the Fe2+ quantum yield but at certain wavelengths, for some ligands this is the opposite. The influence of transient decay pathways and secondary red-ox reactions including interactions with dissolved O-2 has been investigated for Fe(III) glyoxalato complexes using kinetic simulations. Some complexes show a dependence of Fe2+ quantum yield on the irradiation energy. (C) 2013 Published by Elsevier B.V.
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