Magnetic exchange and valence delocalization in a mixed valence [Fe 2+ Fe 3+ Te 2 ] + complex: insights from theory and interpretations of magnetic and spectroscopic data.

A mixed valence binuclear Fe 2.5+ -Fe 2.5+ (Robin-Day Class III) transition metal complex, [Fe 2.5+ μTe 2 Fe 2.5+ ] 1- , composed of two FeN 2 Te 2 pseudo-tetrahedral units with μ-bridging Te 2- ligands was reported to exist in an unprecedented S = 3/2 ground state (Nature Chemistry, https://doi.org/10.1038/s41557-021-00853-5). For this and the homologous complexes containing Se 2- and S 2- , the Anderson-Hasegawa double exchange spin-Hamiltonian was broadly used to interpret the corresponding structural, spectroscopic and magnetic data. First principles multireference ab initio calculations are used here to simulate magnetic and spectroscopic EPR data; analysis of the results affords a rationale for the stabilization of the S = 3/2 ground state of the Fe 2 pair. Complete Active Space Self-Consistent Field (CASSCF) calculations and dynamical correlation accounted for by means of N-Electron Valence Perturbation Theory to Second Order (NEVPT2) reproduce well the g -factors determined from simulations of X-band EPR spectra. A crucial technical tool to achieve these results is: (i) use of a localized orbital formulation of the many-particle problem at the scalar-relativistic CASSCF step; (ii) choice of state averaging over states of a given spin (at the CASCI/NEVPT2 step); and (iii) accounting for spin-orbit coupling within the non-relativistic Born-Oppenheimer (BO) many-particle basis using Quasi-Degenerate Perturbation Theory (QDPT). The inclusion of the S = 5/2 spin manifold reproduced the observed increase in the magnetic susceptibility ( χT ) in the high temperature range ( T > 100 K), which is explained by thermal population of the S = 5/2 excited state at energy 160 cm -1 above the S = 3/2 ground state. Theoretical values of χT from experimentally reported data points in the temperature range from 3 to 30 K were further computed and analyzed using a model which takes spin-phonon coupling into account. The model considerations and the computational protocols of this study are generally applicable to any Class I/II mixed valence dimer. The work can potentially stimulate further experimental and theoretical work on bi- and oligonuclear transition metal complexes of importance to bioinorganic chemistry and life sciences.