Magnetic Properties of High-Nuclearity Fe-oxo (x = 7, 22, 24) Clusters Analyzed by a Multipronged Experimental, Computational, and Magnetostructural Correlation Approach

The synthesis, structure, and magnetic properties of three related iron(III)-oxo clusters are reported, [Fe₇O₃(O₂CPh)₉(mda)₃(H₂O)] (1), [Fe₂₂O₁₄(OH)₃(O₂CMe)₂₁(mda)₆](ClO₄)₂ (2), and [Fe₂₄O₁₅(OH)₄(OEt)(O₂CMe)₂₁(mda)₇](ClO₄)₂ (3), where mdaH₂ is N-methyldiethanolamine. 1 was prepared from the reaction of [Fe₃O(O₂CPh)₆(H₂O)₃](NO₃) with mdaH₂ in a 1:2 ratio in MeCN, whereas 2 and 3 were prepared from the reaction of FeCl₃/NaO₂CMe/mdaH₂ in a 2:∼13:2 ratio and FeCl₃/NaO₂CMe/mdaH₂/pyridine in a 2:∼13:2:25 ratio, respectively, both in EtOH. The core of 1 consists of a central octahedral Fe^III ion held within a nonplanar Fe₆ loop by three μ₃-O^2- and three μ₂-RO^- arms from the three mda^2- chelates. The cores of the cations of 2 and 3 consist of an A:B:A three-layer topology, in which a central Fe₆ (2) or Fe₈ (3) layer B is sandwiched between two Fe₈ layers A. The A layers structurally resemble 1 with the additional Fe added at the center to retain virtual C₃ symmetry. The central Fe₆ layer B of 2 consists of a {Fe₄(μ₄-O)₂(μ₃-OH)₂}⁶⁺ cubane with an Fe on either side attached to cubane O^2- ions, whereas that of 3 has the same cubane but with an {Fe₃(μ₃-O)(μ-OH)} unit attached on one side and a single Fe on the other. Variable-temperature dc and ac magnetic susceptibility studies revealed dominant antiferromagnetic coupling in all complexes leading to ground-state spins of S = ⁵/₂ for 1 and S = 0 for 2 and 3. All Fe₂ pairwise exchange parameters (J) for 1-3 were estimated by two independent methods: density functional theory (DFT) calculations using broken symmetry methods and a magnetostructural correlation previously developed for high-nuclearity Fe^III/O complexes. The two approaches gave satisfyingly similar J values, and the latter allowed rationalization of the experimental ground states by identification of the spin frustration effects operative and the resultant relative spin vector alignments at each Fe^III ion.