Tetra-, penta- and hexacoordinate copper(II) complexes with N3 donor isoindoline-based ligands: Characterization and SOD-like activity

Reaction of 1,3-bis(2′-Ar-imino)isoindolines (HLⁿ, n = 1-7, Ar = benzimidazolyl, N-methylbenzimidazolyl, thiazolyl, pyridyl, 3-methylpyridyl, 4-methylpyridyl, and benzthiazolyl, respectively) with Cu(OCH₃)₂ yields mononuclear hexacoordinate complexes with Cu(Lⁿ)₂ composition. With cupric perchlorate square-pyramidal Cu^II(HLⁿ)(NCCH₃)(OClO₃)]ClO₄ complexes (n = 1, 3, 4) were isolated as perchlorate salts, whereas with chloride Cu^II(HLⁿ)Cl₂ (n = 1, 4), or square-planar Cu^IICl₂(HLⁿ) (n = 2, 3, 7) complexes are formed. The X-ray crystal structures of Cu(L³)₂, Cu(L⁵)₂, Cu^II(HL⁴)(NCCH₃)(OClO₃)]ClO₄, Cu^IICl(L²) and Cu^IICl(L⁷) are presented along with electrochemical and spectral (UV-Vis, FT-IR and X-band EPR) characterization for each compound. When combined with base, the isoindoline ligands in the Cu^II(HLⁿ)(NCCH₃)(OClO₃)]ClO₄ complexes undergo deprotonation in solution that is reversible and induces UV-Vis spectral changes. Equilibrium constants for the dissociation are calculated. X-band EPR measurements in frozen solution show that the geometry of the complexes is similar to the corresponding X-ray crystallographic structures. The superoxide scavenging activity of the compounds determined from the McCord-Fridovich experiment show dependence on structural features and reduction potentials.