Influence of F-position and solvent on coordination geometry and single ion magnet behavior of Co(ii) complexes

Abstract

Three mononuclear Co(II) complexes with the compositions of [Co(L₁)₂] (1), [Co(L₂)₂(CH₃CN)] (2) and [Co(L₃)₂] (3) (HL₁ = 2-((E)-(2-fluorobenzylimino)methyl)-4,6-dibromophenol, HL₂ = 2-((E)-(3-fluorobenzylimino)methyl)-4,6-dibromophenol and HL₃ = 2-((E)-(4-fluorobenzylimino)methyl)-4,6-dibromophenol) were prepared and structurally determined. The changes in the F-positions in the ligands and solvents led to the formation of these products with various coordination geometries. Both complexes 1 and 3 are four-coordinated and their coordination geometries can be described as tetrahedron and seesaw, whereas complex 2 is five coordinated with a coordination configuration in between trigonal bipyramid and square pyramid. Static magnetic studies reveal that all these complexes exhibit considerable easy-axis magnetic anisotropy. The easy-axis magnetic anisotropy of 1 and 3 mainly derives from the first quartet excited state, whereas that of 2 primarily originates from the first, third and fourth quartet excited states established by theoretical calculations. All the resulting complexes display field-induced slow magnetic relaxation. Complex 3 represents the first Co(II) single ion magnet with a seesaw coordination geometry. Ab initio calculations predict that the magnetic anisotropy will enhance when the seesaw coordination geometry varies from distortion to regulation.