Synthesis, Characterization, and Study of Octanuclear Iron-Oxo Clusters Containing a Redox-Active Fe4O4-Cubane Core
journal contributionposted on 21.01.2008, 00:00 by Peter Baran, Roman Boča, Indranil Chakraborty, John Giapintzakis, Radovan Herchel, Qing Huang, John E. McGrady, Raphael G. Raptis, Yiannis Sanakis, Athanasios Simopoulos
A one-pot synthetic procedure yields the octanuclear FeIII complexes Fe8(μ4-O)4(μ-pz*)12X4, where X = Cl and pz* = pyrazolate anion (pz = C3H3N2-) (1), 4-Cl-pz (2), and 4-Me-pz (3) or X = Br and pz* = pz (4). The crystal structures of complexes 1−4, determined by X-ray diffraction, show an Fe4O4-cubane core encapsulated in a shell composed of four interwoven Fe(μ-pz*)3X units. Complexes 1−4 have been characterized by 1H NMR, infrared, and Raman spectroscopies. Mössbauer spectroscopic analysis distinguishes the cubane and outer FeIII centers by their different isomer shift and quadrupole splitting values. Electrochemical analyses by cyclic voltammetry show four consecutive, closely spaced, reversible reduction processes for each of the four complexes. Magnetic susceptibility studies, corroborated by density functional theory calculations, reveal weak antiferromagnetic coupling among the four cubane Fe centers and strong antiferromagnetic coupling between cubane and outer Fe atoms of 1. The structural similarity between the antiferromagnetic Fe8(μ4-O)4 core of 1−4 and the antiferromagnetic units contained in the minerals ferrihydrite and maghemite is demonstrated by X-ray and Mössbauer data.
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isomer shiftRaman spectroscopiescubane Fe centerspyrazolate aniontheory calculations3Hprocedure yields1 H NMRquadrupole splitting valuesreduction processesminerals ferrihydritecyclic voltammetry showM össbauer datam össbauer spectroscopic analysispzFe 4O core encapsulatedantiferromagnetic unitsElectrochemical analysesMagnetic susceptibility studiesFe atomscrystal structurescomplexFeIII centers