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

Abstract

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 FeIII ion held within a nonplanar Fe6 loop by three μ3-O2- and three μ2-RO- arms from the three mda2- 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 O2- 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 (Jij) 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 FeIII/O complexes. The two approaches gave satisfyingly similar Jij 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 FeIII ion.