Metalloporphyrin Mixed-Valence π-Cation Radicals: [Fe(oxoOEC•/2)(Cl)]2SbCl6, Structure, Magnetic Properties, and Near-IR Spectra

The preparation and characterization of a mixed-valence π-cation radical derivative of an iron(III) oxochlorinato complex is reported. The new complex has been synthesized by the one-electron oxidation of a pair of [Fe(oxoOEC)(Cl)] molecules to form the dimeric cation [Fe(oxoOEC)(Cl)]2 +. The cation...

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Bibliographic Details
Published in:Inorganic chemistry 2011-09, Vol.50 (18), p.9114-9121
Main Authors: Li, Ming, Neal, Teresa J, Wyllie, Graeme R. A, Oliver, Allen G, Schulz, Charles E, Scheidt, W. Robert
Format: Article
Language:English
Subjects:
Cations - chemistry
Crystallography, X-Ray
Electron Spin Resonance Spectroscopy
Free Radicals - chemistry
Magnetic Phenomena
Metalloporphyrins - chemistry
Models, Molecular
Spectroscopy, Mossbauer
Spectroscopy, Near-Infrared
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Summary:The preparation and characterization of a mixed-valence π-cation radical derivative of an iron(III) oxochlorinato complex is reported. The new complex has been synthesized by the one-electron oxidation of a pair of [Fe(oxoOEC)(Cl)] molecules to form the dimeric cation [Fe(oxoOEC)(Cl)]2 +. The cation has been characterized by X-ray analysis, Mössbauer spectroscopy, UV–vis and near-IR spectroscopy, and magnetic susceptibility measurements from 6–300 K. The crystal structure shows that the two rings have a smaller overlap area than those of the formally related nickel and copper octaethylporphinate derivatives, reflecting the larger steric congestion at the periphery in part of the oxochlorin rings. The Mössbauer data is consistent with two equivalent iron(III) centers. The unpaired electron is delocalized over the two oxochlorin rings and mediates a strong antiferromagnetic interaction between the high-spin iron(III) centers.
ISSN:0020-1669
1520-510X
DOI:10.1021/ic201292t