A Mixed-Valent Polyiron Oxo Complex that Models the Biomineralization of the Ferritin Core

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Abstract
A novel polyiron oxo complex, [FeIII4FeII8(O)2(OCH3)18(O2CCH3)6(CH3OH) 4.67] (1), has been prepared from ferrous acetate and lithium methoxide in methanol by slow addition of dioxygen. The three-dimensional close-packed layered structure found in 1 closely mimics that proposed for the inorganic core in the iron storage protein ferritin. The Mossbauer spectra of 1 reveal superparamagnetic relaxation at temperatures below 15 K, a property characteristic of the ferritin core. The small size and mixed-valent nature of 1 suggest that it is a reasonable model for intermediates formed in the biomineralization of iron during ferritin core formation. A related compound, with the same iron-oxygen framework found in 1 but containing only two ferric ions, has also been structurally characterized. Because the clusters exhibit properties of both discrete molecules and extended solids, they are representative of a new class of nanometer-sized compounds that bridge the molecular solid-state boundary.