Molecular Structures of Five-Coordinated Halide Ligated Iron(III) Porphyrin, Porphycene, and Corrphycene Complexes

Molecular structures of 12 porphyrin analogues, FeIII(EtioP)X(1 a −1 d ), FeIII(EtioCn)X(2 a −2 d ), and FeIII(Etio-Pc)X(3 a −3 d ), where X = F (a), Cl (b), Br (c), and I (d), are determined on the basis of X-ray crystallography. Combined analyses using Mössbauer, 1H NMR, and EPR spectroscopy as we...

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Veröffentlicht in:Inorganic chemistry 2002-09, Vol.41 (18), p.4627-4629
Hauptverfasser: Ohgo, Yoshiki, Neya, Saburo, Ikeue, Takahisa, Takahashi, Masashi, Takeda, Masuo, Funasaki, Noriaki, Nakamura, Mikio
Format: Artikel
Sprache:eng
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Zusammenfassung:Molecular structures of 12 porphyrin analogues, FeIII(EtioP)X(1 a −1 d ), FeIII(EtioCn)X(2 a −2 d ), and FeIII(Etio-Pc)X(3 a −3 d ), where X = F (a), Cl (b), Br (c), and I (d), are determined on the basis of X-ray crystallography. Combined analyses using Mössbauer, 1H NMR, and EPR spectroscopy as well as SQUID magnetometry have revealed that 3 d exhibits a quite pure S = 3/2 spin state with a small amount of an S = 5/2 spin admixture. In contrast, all the other complexes show the S = 5/2 spin state with a small amount of the S = 3/2 spin admixture. The structural and spectroscopic data indicate a strong correlation between the spin states of the complexes and the core geometries such as Fe−N bond lengths, cavity areas, and ΔFe values.
ISSN:0020-1669
1520-510X
DOI:10.1021/ic0256866