L-edge X-ray absorption and X-ray magnetic circular dichroism of oxygen-bridged dinuclear iron complexes

G. Peng, J. Van Elp, H. Jang, L. Que, Ho Gyeom Jang, S. P. Cramer

Research output: Contribution to journalArticle

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Abstract

Iron L-edge X-ray absorption and X-ray magnetic circular dichroism (XMCD) spectroscopy have been used to study the electronic structure of dinuclear iron - oxo complexes with different types of magnetic and electronic interactions between the iron sites. Trapped-valence systems exhibit L-edges with clear multiplet structure. The L-edges of trapped-valence FeIIFeIII complexes such as [FeIII,II 2(salmp)2]- and [Fe2 III,II(bpmp)(μ-O2CC2H 5)2]2- can be interpreted as the sum of distinct Fe(II) and Fe(III) component spectra. Furthermore, an atomic multiplet theory including adjustable ligand field splittings can successfully simulate the Fe(II) and Fe(III) X-ray absorption. Reasonable ligand field parameters are obtained by optimizing the correspondence between calculated and experimental spectra. The XMCD for the [Fe2 III,II(bpmp)(μ-O2CC2H 5)2]2- complex is also reported; it exhibits an interesting magnetic field dependence that reflects the weak magnetic coupling between Fe(II) and Fe(III) ions. In contrast with the trapped-valence complex spectra, the L-edge spectrum for the electronically delocalized complex, [Fe2(Me3tacn)2-(μ-OH)3](BPh 4)2·2MeOH, exhibits a broad L-edge spectrum with poorly resolved multiplet structure. L-edge spectroscopy is capable of characterizing electron delocalization on a very fast (femtosecond) time scale, while XMCD is an alternative technique for characterizing exchange interactions.

Original languageEnglish
Pages (from-to)2515-2519
Number of pages5
JournalJournal of the American Chemical Society
Volume117
Issue number9
Publication statusPublished - 1995 Mar 8
Externally publishedYes

Fingerprint

X ray absorption
Dichroism
Circular Dichroism
Iron
X-Rays
Oxygen
X rays
Ligands
Circular dichroism spectroscopy
Magnetic couplings
Exchange interactions
Spectrum Analysis
Electronic structure
Spectroscopy
Ions
Magnetic fields
Magnetic Fields
Electrons

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

L-edge X-ray absorption and X-ray magnetic circular dichroism of oxygen-bridged dinuclear iron complexes. / Peng, G.; Van Elp, J.; Jang, H.; Que, L.; Jang, Ho Gyeom; Cramer, S. P.

In: Journal of the American Chemical Society, Vol. 117, No. 9, 08.03.1995, p. 2515-2519.

Research output: Contribution to journalArticle

Peng, G. ; Van Elp, J. ; Jang, H. ; Que, L. ; Jang, Ho Gyeom ; Cramer, S. P. / L-edge X-ray absorption and X-ray magnetic circular dichroism of oxygen-bridged dinuclear iron complexes. In: Journal of the American Chemical Society. 1995 ; Vol. 117, No. 9. pp. 2515-2519.
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