Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 132, Issue 51, Pages 17983-17985Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ja107374s
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- Department of Science and Technology, Government of India
- CSIR, New Delhi
- CSIR, India
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A novel diiron(III) bisporphyrin bridged by a hydroxo group between two cofacial Fe centers is reported. X-ray structural characterization revealed the remarkably bent mu-hydroxobis[Fe(III) porphyrin] with the smallest known Fe-O(H)-Fe angle [142.5(2)degrees] reported to date in an iron porphyrin. The close approach of the two rings in the molecule results in an unequal core deformation, and as a result, the geometrical parameters (such as the Fe-N-p, Fe-O and Fe center dot center dot center dot Ct(p) distances) are all different for the two Fe(III) centers, leading for the first time to a natural way of stabilizing two different spins of iron in a single molecular framework with complete retention of their own spectroscopic identities in both the solid state and solution. The strong antiferromagnetic coupling between the two Fe(III) centers in the mu-oxo dimer (-J = 126.6 cm(-1)) is attenuated to only 4.5 cm(-1) simply by protonation to give the,mu-hydroxo complex.
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