Impact of Halogenido Coligands on Magnetic Anisotropy in Seven-Coordinate Co(II) Complexes.

The structural and magnetic features of a series of mononuclear seven-coordinate CoII complexes with the general formula [Co(L)X2], where L is a 15-membered pyridine-based macrocyclic ligand (3,12,18-triaza-6,9-dioxabicyclo[12.3.1]octadeca-1(18),14,16-triene) and X = Cl- (1), Br- (2), or I- (3), were investigated experimentally and theoretically in order to reveal how the corresponding halogenido coligands in the apical positions of a distorted pentagonal-bipyramidal coordination polyhedron may affect the magnetic properties of the prepared compounds. The thorough analyses of the magnetic data revealed a large easy-plane type of the magnetic anisotropy (D > 0) for all three compounds, with the D-values increasing in the order 35 cm-1 for 3 (I-), 38 cm-1 for 1 (Cl-), and 41 cm-1 for 2 (Br-). Various theoretical methods like the Angular Overlap Model, density functional theory, CASSCF/CASPT2, CASSCF/NEVPT2 were utilized in order to understand the observed trend in magnetic anisotropy. The D-values correlated well with the Mayer bond order (decreasing in order Co-I > Co-Cl > Co-Br), which could be a consequence of two competing factors: (a) the ligand field splitting and (b) the covalence of the Co-X bond. All the complexes also behave as field-induced single-molecule magnets with the spin reversal barrier Ueff increasing in order 1 (Cl-) < 2 (Br-) < 3 (I-); however, taking into account the easy-plane type of the magnetic anisotropy, the Raman relaxation process is most likely responsible for slow relaxation of the magnetization. The results of the work revealed that the previously suggested and fully accepted strategy employing heavier halogenido ligands in order to increase the magnetic anisotropy has some limitations in the case of pentagonal-bipyramidal CoII complexes.