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Constrained complexes of manganese(II) tetraphenylporphyrin in rigid solution

Journal Article · · J. Phys. Chem.; (United States)
DOI:https://doi.org/10.1021/j100397a039· OSTI ID:6538691
Optical absorption and ESR spectra revealed that chloro- and bromo(tetraphenylporphyrin)manganese(III) (ClMn/sup III/TPP and BrMn/sup III/TPP) in 2-methyltetrahydrofuran (MTHF) solution were reduced to Mn/sup/II/TPP at 77/sup 0/K by ..gamma.. irradiation. The Mn/sup II/TPP species derived from ClMn/sup III/TPP and BrMn/sup III/TPP were found to be different from each other and also from a chemically prepared Mn/sup II/TPP in their absorption and ESR spectra, although all of the Mn/sup II/TpPP species were in the high-spin state (S = 5/2). These spectroscopic data are interpreted in terms of the formation through electron capture during irradiation of constrained complexes of Mn/sup II/TPP in which Mn/sup II/TPP is forced to retain the halide ions in the axial position because of the rigidity of the low-temperature solvent matrix. On the other hand, the chemically prepared Mn/sup II/TPP is regarded as having a solvent molecule weakly coordinating in the axial position.
Research Organization:
Inst. of Physical and Chemical Research, Saitama, Japan
OSTI ID:
6538691
Journal Information:
J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 86:8; ISSN JPCHA
Country of Publication:
United States
Language:
English

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