Magnetic exchange interactions in binuclear and tetranuclear iron(III) complexes described by spin‐flip DFT and Heisenberg effective Hamiltonians

Low‐energy spectra of single‐molecule magnets (SMMs) are often described by Heisenberg Hamiltonians. Within this formalism, exchange interactions between magnetic centers determine the ground‐state multiplicity and energy separation between the ground and excited states. In this contribution, we extract exchange coupling constants (J) for a set of iron (III) binuclear and tetranuclear complexes from all‐electron calculations using non‐collinear spin‐flip time‐dependent density functional theory (NC‐SF‐TDDFT). For 12 binuclear complexes with J‐values ranging from −6 to −132 cm(−1), our benchmark calculations using the short‐range hybrid ωPBEh functional and 6‐31G(d,p) basis set agree well with the experimentally derived values (mean absolute error of 4.7 cm(−1)). For the tetranuclear SMMs, the computed J constants are within 6 cm(−1) from the experimentally derived values. We explore the range of applicability of the Heisenberg model by analyzing bonding patterns in these Fe(III) complexes using natural orbitals (NO), their occupations, and the number of effectively unpaired electrons. The results illustrate the efficiency of the spin‐flip protocol for computing the exchange couplings and the utility of the NO analysis in assessing the validity of effective spin Hamiltonians.