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A Multiplet Analysis of Fe K-Edge 1s → 3d Pre-Edge Features of Iron Complexes
Abstract
X-ray absorption Fe−K edge data on ferrous and ferric model complexes have been studied to establish a detailed understanding of the 1s → 3d pre-edge feature and its sensitivity to the electronic structure of the iron site. The energy position and splitting, and intensity distribution, of the pre-edge feature were found to vary systematically with spin state, oxidation state, geometry, and bridging ligation (for binuclear complexes). A methodology for interpreting the energy splitting and intensity distribution of the 1s → 3d pre-edge features was developed for high-spin ferrous and ferric complexes in octahedral, tetrahedral, and square pyramidal environments and low-spin ferrous and ferric complexes in octahedral environments. In each case, the allowable many-electron excited states were determined using ligand field theory. The energies of the excited states were calculated and compared to the energy splitting in the 1s → 3d pre-edge features. The relative intensities of electric quadrupole transitions into the many-electron excited states were obtained and compared to the intensity pattern of the pre-edge feature. The effects of distorting the octahedral iron site to tetrahedral and square pyramidal geometries were analyzed. The contributions to the pre-edge intensity from both electric quadrupole and electric dipole (from 3d−4p mixing) intensity mechanisms were established for these distorted cases; the amount of 4p character and its distribution over the many-electron final states were experimentally estimated and compared to theoretical predictions from density functional calculations. The methodology was also applied to binuclear complexes, and a clear marker for the presence of a μ-oxo Fe−O−Fe bridge was established. General trends in 3d−4p mixing are developed and discussed for a series of geometries and oxidation states of Fe complexes. The results presented should further aid in the interpretation of the 1s → 3d pre-edge region of iron complexes and non-heme iron enzymes.
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Deng, D., Chen, X., Yu, L., Wu, X., Liu, Q., Liu, Y., Yang, H., Tian, H., Hu, Y., Du, P., et al. (2015) · Science Advances · doi:10.1126/sciadv.1500462 · Cited by 869
He, Y., Hwang, S., Cullen, D. A., Uddin, M. A., Langhorst, L., Li, B., Karakalos, S., Kropf, A. J., Wegener, E. C., Sokolowski, J., et al. (2019) · Energy & Environmental Science · doi:10.1039/c8ee02694g · Cited by 868
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Metadata
- Authors
- Westre, T. E., Kennepohl, P., DeWitt, J. G., Hedman, B., Hodgson, K. O., & Solomon, E. I.
- Venue
- Journal of the American Chemical Society
- Publisher
- American Chemical Society (ACS)
- Published
- 1997-07-01
- Volume
- 119
- Issue
- 27
- Pages
- 6297-6314
- ISSN
- 0002-7863 (ISSN-L)
- 1520-5126
- OpenAlex
- W2078171437
- Cited by
- 1,473
- References
- 0
- FWCI
- 15.99
- Type
- journal article
- Language
- en
- Open access
- closed
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