Copper (II) complexes based on the mixed ligand system: Study of synthesis, characterization, and stopped‐flow kinetics of copper oxidase‐mimicking catalytic activity

Abstract

Two copper (II) complexes based on the mixed ligand system were synthesized and structurally characterized. The molecular formulae for complex ( 1 ), [Cu 2 L 1 L′] and complex ( 2 ), [CuL 2 L′] were determined based on analytical data, molar conductance, and thermal analysis results. The optimized structures of complexes ( 1 ) and ( 2 ) were determined by magnetic and spectroscopic measurements (FTIR, UV–Vis, and ESR) and confirmed by processing powder X‐ray diffraction data by Expo 2014 software. The geometry index ( τ 5 ), determined by ESR spectra and structural analysis based on powder X‐ray, demonstrates the square pyramidal geometry of the Cu (II) center of [Cu 2 L 1 L′] and [CuL 2 L′]. Cyclic voltammetry measurements were performed to elucidate the relationship between the redox properties of ( 1 ) and ( 2 ) and their oxidase‐mimicking catalytic activity. Catalytic aerobic oxidation of the polyphenols 3,5‐di‐tert‐butylcatechol (3,5‐DTBCH 2 ), 4‐nitrocatechol, and 2‐aminophenol (2‐APH 3 ) was studied by stopped‐flow technique. Promising catechol oxidase (COX) and phenoxazinone synthase (PHS) mimetic activity have been demonstrated for ( 1 ) and ( 2 ). Electrochemical data were used to determine the free energy (Δ G °) or driving force (−λ), and their correlation with the oxidase mimetic activity of( 1 ) and ( 2 ) was examined. Several experimental procedures have been performed that have helped describe the catalytic mechanisms of the catalytic reactions taking place.