Modulation of Magnetic Anisotropy and Exchange Interaction in Phenoxide-Bridged Dinuclear Co(II) Complexes

We report a new class of four dimeric Co(II) complexes [Co₂(bbpen)(X)₂] (H₂bbpen = N,N'-bis(2-hydroxybenzyl)-N,N'-bis(2-methylpyridyl)ethylenediamine) [X^- = SCN (1), Cl (2), Br (3), and I (4)] with different coordination geometry of two Co(II) centers (trigonal-prismatic and pseudo-tetrahedral) and their magnetic study. Interestingly, the two Co(II) centers show two different types of magnetic anisotropy. State of the art ab initio CASSCF analysis reveals that the six-coordinate or the trigonal-prismatic Co(II) center possesses a consistently large negative axial zero-field splitting (negative D) parameter (∼-60 cm^-1), while the four-coordinate or the pseudo-tetrahedral Co(II) center exhibits a range of D values from +13 to -23 cm^-1. Ab initio calculations employing the lines model were used to estimate the magnetic exchange as both the Co(II) centers possess significant magnetic anisotropy. All the complexes display rare ferromagnetic interaction, and the strength of this interaction decreases as the ligand field on the pseudo-tetrahedral Co(II) center decreases from SCN^- > Cl^- > Br^- > I^-.