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Published March 3, 2008 | Version Supplemental Material
Journal Article Open

X-ray photochemistry in iron complexes from Fe(0) to Fe(IV) – Can a bug become a feature?

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Abstract

Under intense soft X-ray irradiation, we have observed time-dependent changes in the soft X-ray spectra of virtually all the Fe coordination complexes that we have examined, indicating chemical transformation of the compound under study. Each compound, with oxidation states ranging from Fe(IV) to Fe(0), has been studied with either Fe L-edge spectroscopy or N K-edge spectroscopy. We find that very often a well-defined spectroscopic change occurs, at least initially, which is apparently capable of straightforward interpretation in terms of X-ray induced photoreduction, photooxidation or ligand photolysis. We briefly discuss the probable chemical nature of the changes and then estimate the rate of chemical change, thereby establishing the necessary radiation dose. We also demonstrate that the photochemistry not only depends on the Fe oxidation state but also the coordination chemistry of the complex. It seems that a proper understanding of such X-ray photochemical effects could well greatly assist the assignment of soft X-ray spectra of uncharacterized metal sites.

Additional Information

© 2007 Elsevier B.V. Received 19 October 2007; accepted 28 October 2007. Available online 4 November 2007. Dedicated to Edward Solomon. One of us (S.P.C.) would especially like to thank Ed Solomon for hosting him during 'minisabbaticals' at Stanford. The group meetings were always intellectually stimulating, and the frequent birthday cakes were a special treat. We thank the ALS staff, in particular Drs. Elke Arenholtz and Anthony Young for their support of beamline 4.0.2. This work was funded by NIH Grant EB-001962 (SPC). ABEX is supported by the DOE Office of Biological and Environmental Research. J.C.P. gratefully acknowledges support from the NSF (CHE-0132216), the DOE (PECASE), and the Alfred P. Sloan Foundation. T.B.R. thanks the NIH (GM-061153) for support. The Advanced Light Source is supported by the DOE Office of Science, Office of Basic Energy Sciences.

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Additional details

Identifiers

Eprint ID
48002
DOI
10.1016/j.ica.2007.10.039
Resolver ID
CaltechAUTHORS:20140805-140326162

Funding

NIH
EB-001962
Department of Energy (DOE) Office of Biological and Environmental Research
NSF
CHE-0132216
Department of Energy (DOE) PECASE
Alfred P. Sloan Foundation
Department of Energy (DOE) Office of Science, Office of Basic Energy Sciences

Dates

Created
2014-08-05
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Updated
2021-11-10
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