Molecular structures of five-coordinated halide ligated iron(III) porphyrin, porphycene, and corrphycene complexes.
Molecular structures of 12 porphyrin analogues, Fe(III)(EtioP)X(1(a)-1(d)), Fe(III)(EtioCn)X(2(a)-2(d)), and Fe(III)(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, (1)H 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 DeltaFe values.
Department of Chemistry, School of Medicine, Toho University, Ota-ku, Tokyo 143-8540, Japan.
Yoshiki
Y
Ohgo
Saburo
S
Neya
Takahisa
T
Ikeue
Masashi
M
Takahashi
Masuo
M
Takeda
Noriaki
N
Funasaki
Mikio
M
Nakamura