A Trinuclear High-Spin Iron(III) Complex with a Geometrically Frustrated Spin Ground State Featuring Negligible Magnetic Anisotropy and Antisymmetric Exchange

The trinuclear high-spin iron(III) complex [Fe₃Cl₃(saltag^Br)(py)₆]ClO₄ {H₅saltag^Br = 1,2,3-tris[(5-bromo-salicylidene)amino]guanidine} was synthesized and characterized by several experimental and theoretical methods. The iron(III) complex exhibits molecular 3-fold symmetry imposed by the rigid ligand backbone and crystallizes in trigonal space group P3̅ with the complex cation lying on a crystallographic C₃ axis. The high-spin states (S = ⁵/₂) of the individual iron(III) ions were determined by Mösbauer spectroscopy and confirmed by CASSCF/CASPT2 ab initio calculations. Magnetic measurements show an antiferromagnetic exchange between the iron(III) ions leading to a geometrically spin-frustrated ground state. This was complemented by high-field magnetization experiments up to 60 T, which confirm the isotropic nature of the magnetic exchange and negligible single-ion anisotropy for the iron(III) ions. Muon-spin relaxation experiments were performed and further prove the isotropic nature of the coupled spin ground state and the presence of isolated paramagnetic molecular systems with negligible intermolecular interactions down to 20 mK. Broken-symmetry density functional theory calculations are consistent with the antiferromagnetic exchange between the iron(III) ions within the presented trinuclear high-spin iron(III) complex. Ab initio calculations further support the absence of appreciable magnetic anisotropy (D = 0.086, and E = 0.010 cm⁻¹) and the absence of significant contributions from antisymmetric exchange, as the two Kramers doublets are virtually degenerate (ΔE = 0.005 cm⁻¹). Therefore, this trinuclear high-spin iron(III) complex should be an ideal candidate for further investigations of spin-electric effects arising exclusively from the spin chirality of a geometrically frustrated S = ¹/₂ spin ground state of the molecular system.