Issue 44, 2021

Ultrafast photoelectron spectroscopy of photoexcited aqueous ferrioxalate

Abstract

The photochemistry of metal–organic compounds in solution is determined by both intra- and inter-molecular relaxation processes after photoexcitation. Understanding its prime mechanisms is crucial to optimise the reactive paths and control their outcome. Here we investigate the photoinduced dynamics of aqueous ferrioxalate ([FeIII(C2O4)3]3−) upon 263 nm excitation using ultrafast liquid phase photoelectron spectroscopy (PES). The initial step is found to be a ligand-to-metal electron transfer, occuring on a time scale faster than our time resolution (≲30 fs). Furthermore, we observe that about 25% of the initially formed ferrous species population are lost in ∼2 ps. Cast in the contest of previous ultrafast infrared and X-ray spectroscopic studies, we suggest that upon prompt photoreduction of the metal centre, the excited molecules dissociate in <140 fs into the pair of CO2 and [(CO2)FeII(C2O4)2]3− fragments, with unity quantum yield. About 25% of these pairs geminately recombine in ∼2 ps, due to interaction with the solvent molecules, reforming the ground state of the parent ferric molecule.

Graphical abstract: Ultrafast photoelectron spectroscopy of photoexcited aqueous ferrioxalate

Supplementary files

Article information

Article type
Paper
Submitted
24 Jun 2021
Accepted
21 Oct 2021
First published
21 Oct 2021

Phys. Chem. Chem. Phys., 2021,23, 25308-25316

Ultrafast photoelectron spectroscopy of photoexcited aqueous ferrioxalate

L. Longetti, T. R. Barillot, M. Puppin, J. Ojeda, L. Poletto, F. van Mourik, C. A. Arrell and M. Chergui, Phys. Chem. Chem. Phys., 2021, 23, 25308 DOI: 10.1039/D1CP02872C

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