Abstract
Mössbauer spectra of a polycrystalline form of oxidized chloro-5,10,15,20-tetra(mesityl)porphyrin- atoiron(III) [Fe(TMP)Cl], compound A, were recorded over a range of temperatures (4.2–195 K) and magnetic fields (0–6 T). These spectra of compound A exhibit magnetic features which are markedly different from those of the analogous protein complexes, horse radish peroxidase compound I (HRP-I) and compound ES of cytochrome c peroxidase, even though chemical evidence and optical spectroscopy indicate that compound A is similar to the others in comprising a Fe(IV) complex within a porphyrin cation radical. We interpret the data by employing a spin Hamiltonian model in which the central Fe(IV) complex, with S=1, is tightly coupled to a S=1/2 system of the oxidized porphyrin to yield a net S=3/2 system as suggested by the susceptibility measurements. The theoretical treatment yields information on the d-electron energies which is similar to that more directly available in the peroxidase spectra. The strength of the axial crystal field is found to increase progressively in the series HRP-I, ES, compound A, while the spin coupling in A is the strongest of the three by several orders of magnitude. The good fits to experimental data confirm the efficacy of the theoretical treatment which may be applicable to a variety of other coupled systems.
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Dates
Type | When |
---|---|
Created | 22 years, 6 months ago (Feb. 28, 2003, 12:03 p.m.) |
Deposited | 1 year, 6 months ago (Feb. 9, 2024, 8:06 p.m.) |
Indexed | 5 months, 2 weeks ago (March 19, 2025, 9:07 a.m.) |
Issued | 42 years, 1 month ago (Aug. 1, 1983) |
Published | 42 years, 1 month ago (Aug. 1, 1983) |
Published Print | 42 years, 1 month ago (Aug. 1, 1983) |
@article{Boso_1983, title={Mössbauer effect study of tight spin coupling in oxidized chloro-5,10,15,20-tetra(mesityl)porphyrinatoiron(III)}, volume={79}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.445913}, DOI={10.1063/1.445913}, number={3}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Boso, Brian and Lang, George and McMurry, Thomas J. and Groves, John T.}, year={1983}, month=aug, pages={1122–1126} }