Phenoxazinyl Zn(ii) diradical complex formed via redox-driven cyclization of a 2-aminophenol-based N3O ligand. Isolation of the modified N3 ligand radical and its Ni(ii) complex

Abstract

Aerobic reaction between the pyridine-2-carboxamide-2-aminophenol N₃O ligand (H₃L¹) and Zn(ClO₄)₂·6H₂O in CH₃CN affords an N₃ phenoxazinylate coordinated Zn(II) complex; its diradical electronic structure [Zn^II{(L¹*)˙⁻}₂] has been elucidated from redox, spectroscopic (UV-VIS and EPR), and magnetic measurements and DFT calculations. Isolation and characterization of the metal-assisted redox-driven modified N₃ ligand as a radical cation (H₂L¹*)˙⁺ and its Ni(II)-diradical complex [Ni^II{(L¹*)˙⁻}₂] have also been achieved.