Theoretical Insights into the Magnetostructural Correlations in Mn3-Based Single-Molecule Magnets

Density functional theory (DFT) and the valence bond configuration interaction (VBCI) model have been applied to the oximato-based MnIII3O single-molecule magnets (SMMs), allowing one to correlate the MnIII−MnIII exchange coupling energy (J) with the bridging geometry in terms of two structural angles: the Mn−O−N−Mn torsion angle (γ) and the Mn3 out-of-plane shift of O (angle δθ). Using DFT, a two-dimensional (γ, δθ) energy surface of J is derived and shown to yield essentially good agreement with the reported J values deduced from magnetic susceptibility data on trigonal oximato-bridged Mn3 SMMs. VBCI is used to understand and analyze the DFT results. It is shown that the exchange coupling in these systems is governed by a spin-polarization mechanism inducing a pronounced and dominating ferromagnetic exchange via the oximato bridge as opposed to kinetic exchange, which favors a weaker and antiferromagnetic exchange via the bridging oxide. In the light of these results, a discussion of the exchange coupling in the Mn6 family of the SMM with a record demagnetization barrier is given.