Cobalt and nickel homobinuclear metallomacrocycles based on the redox-active bis-semiquinonato ligands as potential functional absorbing materials

Abstract

Recently obtained bis-o-quinone with resorcinol as a bridge was utilized for synthesis of cobalt and nickel homobinuclear complexes. Two bis-o-semiquinonato metal fragments are situated co-facially to each other forming metallomacrocycle. Metals in both fragments bond diethyl ether solvate molecules externally as well as internally in the cell. At 100 K one of two metal atoms in the macrocycle is five-coordinated whereas the other one is six-coordinated due to internal solvent molecule. Heating to room temperature results in disordering of internal solvent molecule in two positions: coordinated to different nickel atoms. Variable temperature magnetic measurements indicate both complexes to be bis-o-semiquinonato anion-radical adducts of high spin metals with magnetic interactions inside of bis-o-semiquinonato units. Sign and energy of interactions depend on the coordination number of metal. Exchange interactions between units are weak. UV–Vis absorption spectrum is determined by ligands centered bands. CV indicates reversible reduction processes involving redox active dioxolene ligands.