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Published online by Cambridge University Press: 25 February 2011
Nanometer-sized molecular complexes of superexchange-coupled iron ions with iron nuclearity n < 10 exhibit short-range intramolecular magnetic ordering and ‘particlelike’ superparamagnetism in their low temperature Mössbauer spectra. A comparative study of the magnetic properties of ca 10 Å diameter iron-oxo phases obtained through controlled hydrolytic polymerization of iron in non-aqueous solvents is presented. The magnetic anisotropy energy constant, K, which is proportional to the observed blocking temperature, T B , and the sharpness of the superparamagnetic transition depend critically on the iron oxidation state and degree of 3d-electron delocalization. Representative examples of mixed-valent iron complexes containing oxo-bridged, octahedrally coordinated iron with primarily either Fe(III) or Fe(II) character are discussed.