Stereochemistry of coordination polyhedra <i>vs.</i> single ion magnetism in penta- and hexacoordinated Co(<scp>ii</scp>) complexes with tridentate rigid ligands

Abstract

A tridentate ligand L (2,6-bis(1-(3,5-di-tert-butylbenzyl)-1H-benzimidazol-2-yl)pyridine) was synthesized and used for the preparation of three pentacoordinated Co(ii) complexes of formula [Co(L)X₂] (where X = NCS^- for 1, X = Cl^- for 2 and X = Br^- for 3) and one ionic compound 4 ([Co(L)₂]Br₂·2CH₃OH·H₂O) containing a hexacoordinated Co(ii) centre. Static magnetic data were analysed with respect to the spin (1-3) or the Griffith-Figgis (4) Hamiltonian. Ab initio calculations enable us to identify the positive axial magnetic anisotropy parameter D accompanied by a significant degree of rhombicity in the reported complexes. Also, magneto-structural correlation was outlined for this class of compounds. Moreover, all four compounds exhibit slow relaxation of magnetisation at an applied static magnetic field with either both low- and high-frequency relaxation channels (3) or a single high-frequency relaxation process (1, 2 and 4). The interplay between the stereochemistry of coordination polyhedra, magnetic anisotropy and the relaxation processes was investigated and discussed in detail.