Cobalt(ii) coordination to an N4-acenaphthene-based ligand and its sodium complex

Abstract

A new bifunctional N₄-ligand was obtained via the condensation reaction of acenaphthenequinone and 2-picolylamine. A peculiarity of this synthesis is the formation of a new intramolecular C–C bond during the reaction. The structure and redox properties of the ligand were studied. The anion-radical form of the ligand was prepared via the chemical reduction of the latter with metallic sodium as well as in situ via its electrochemical reduction in a solution. The sodium salt prepared was structurally characterized using single-crystal X-ray diffraction (XRD). New cobalt complexes with the ligand in neutral and anion-radical forms were synthesized and further studied. As a result, three new homo- and heteroleptic cobalt(II) complexes were obtained, in which the cobalt atom demonstrates different modes of coordination with the ligand. Cobalt(II) complex CoL₂ with two monoanionic ligands was prepared by the electrochemical reduction of a related L₂CoBr₂ complex or by treating cobalt(II) bromide with the sodium salt. XRD was used to study the structures of all cobalt complexes prepared. Magnetic and electron paramagnetic resonance studies were performed: Co^II ion states with S = 3/2 and S = 1/2 were found for the complexes. A quantum-chemical study confirmed that the spin density is mainly located at the cobalt center.