Ultraviolet photochemical reaction of [Fe(III)(C2O4)3]3? in aqueous solutions studied by femtosecond time-resolved X-ray absorption spectroscopy using an X-ray free electron laser

摘要

Time-resolved X-ray absorption spectroscopy was performed for aqueous ammonium iron(III) oxalate trihydrate solutions using an X-ray free electron laser and a synchronized ultraviolet laser. The spectral and time resolutions of the experiment were 1.3?eV and 200 fs, respectively. A femtosecond 268?nm pulse was employed to excite [Fe(III)(C₂O₄)₃]3? in solution from the high-spin ground electronic state to ligand-to-metal charge transfer state(s), and the subsequent dynamics were studied by observing the time-evolution of the X-ray absorption spectrum near the Fe K-edge. Upon 268?nm photoexcitation, the Fe K-edge underwent a red-shift by more than 4?eV within 140 fs; however, the magnitude of the redshift subsequently diminished within 3 ps. The Fe K-edge of the photoproduct remained lower in energy than that of [Fe(III)(C₂O₄)₃]3?. The observed red-shift of the Fe K-edge and the spectral feature of the product indicate that Fe(III) is upon excitation immediately photoreduced to Fe(II), followed by ligand dissociation from Fe(II). Based on a comparison of the X-ray absorption spectra with density functional theory calculations, we propose that the dissociation proceeds in two steps, forming first [(CO₂?)Fe(II)(C₂O₄)₂]3? and subsequently [Fe(II)(C₂O₄)₂]2?.