Iron(iii) bis(pyrazol-1-yl)acetate based decanuclear metallacycles: synthesis, structure, magnetic properties and DFT calculations

Abstract

The synthesis, structural aspects, magnetic interpretation and theoretical rationalizations for a new member of the ferric wheel family, a decanuclear iron(III) complex with the formula [Fe₁₀(bdtbpza)₁₀(μ₂-OCH₃)₂₀] (1), featuring the N,N,O tridentate bis(3,5-di-tert-butylpyrazol-1-yl)acetate ligand, are reported. The influence of the steric effect on both the core geometry and coordination mode is observed. Temperature dependent (2.0–300 K range) magnetic susceptibility studies carried out on complexes 1 established unequivocally antiferromagnetic (AF) interactions between high-spin iron(III) centers (S = 5/2), leading to a ground state S = 0. The mechanism of AF intramolecular coupling was proved using a broken-symmetry approach within the density functional method at the B3LYP/def2-TZVP(-f)/def2-SVP level of theory.