Structural, Spectroscopic, and Theoretical Investigation of a T-Shaped [Fe3(μ3-O)] Cluster

The synthesis, X-ray crystal and electronic structures of [Fe3(μ3-O)(mpmae)2(OAc)2 Cl3], 1, where mpmae-H = 2-(N-methyl-N-((pyridine-2-yl)methyl)amino)ethanol, are described. This cluster comprises three high-spin ferric ions and exhibits a T-shaped site topology. Variable-frequency electron paramagnetic resonance measurements performed on single crystals of 1 demonstrate a total spin ST = 5/2 ground state, characterized by a small, negative, and nearly axial zero-field splitting tensor D = −0.49 cm–1, E/D ≈ 0.055. Analysis of magnetic susceptibility, magnetization, and magneto-structural correlations further corroborate the presence of a sextet ground-spin state. The observed ground state originates from the strong anti-ferromagnetic interaction of two iron(III) spins, with J = 115(5) cm–1, that, in turn, are only weakly coupled to the spin of the third site, with j = 7(1) cm–1. These exchange interactions lead to a ground state with magnetic properties that are essentially entirely determined by the wea...