Probing the dynamic behaviour and magnetic identification of seven coordinated Mn(II) complexes: a combined AIMD and multi-reference approach.

We present an in-depth solution phase dynamics of rare seven coordinated pentagonal bipyramidal Mn(II) complexes, together with their binding affinity anticipated using molecular dynamics (AIMD) simulations and density functional theory (DFT). Moreover, the simulations at different temperatures (25 °C and 90 °C) interpret the rigidity and stability of the ligands with Mn(II) ions. An intuitive approach for modulating the easy plane magnetic anisotropy of the mononuclear Mn(II) complex has been revealed by this work. In this regard, we have performed an extensive theoretical study based on the CASSCF/NEVPT2 method, exhibiting the presence of an easy plane magnetic anisotropy with a positive value of axial zero-field splitting (ZFS) parameter . The complex's magnetic properties and electronic relaxation reveal that the rhombic ZFS term () can be modulated as the symmetry around the Mn(II) ion varies. The magnitude of the -value increased with a more symmetrical equatorial ligand as found in the order of [Mn(pydpa)(HO)] > [Mn(cbda)(HO)] > [Mn(dpaaa)(HO)] > [Mn(dpasam)(HO)]. Furthermore, we found that substituting the equatorial oxygen atom with heavier S and Se-donor atoms switches the sign of magnetic anisotropy for the Mn(II) complexes. The magnitude of the -value increased when the energy levels of the ground state (GS) and the first excited state (ES) decreased. The observed magneto-structural correlation reveals that shortening the distance of the axial water molecule (Mn-O(w)) increases the -value by an order of magnitude for the symmetrical [Mn(pydpa)(HO)] complex. Overall, the combined analysis of solution phase dynamics of Mn(II) complexes and their magnetic characterization opens up new avenues in coordination chemistry, molecular magnetism, spin-crossover materials, and catalysis.