Ligand-driven redox transformations and catalytic activities of mononuclear copper complexes: structural and spectroscopic insights.

Eight mononuclear complexes have been synthesized, namely: [(L1)Cu]ClO (1), [(L2)Cu]ClO·CHCN (2·CHCN), (L2)Cu(DMF)·2DMF·HO (3·2DMF·HO), (L1)Cu(MeCN) (4), [(L1)Cu(Cl)]PF (5), (tren)Cu(MeCN) (6), [(tren)Cu(Cl)]PF (7) and (L2')Cu(DMF)·DMF·HO (8·DMF·HO). In these complexes, copper atoms are coordinated to tetradentate ligands such as tris-(4-(4-(-butyl))benzyl-3-aza-3-butenyl)amine (L1), tris(2-aminoethyl)amine (tren), tris-(4-pyren-1-yl-3-aza-3-butenyl)amine (L2) and bis-(4-pyren-1-yl-3-aza-3-butenyl)aminoethylamine (L2'). The complexes were structurally characterized by X-ray crystallography, along with various spectroscopic techniques. Complexes 1 and 2 are Cu(I) complexes, exhibiting trigonal pyramidal geometry, whereas complexes 3 to 8 are Cu(II) complexes with distorted trigonal bipyramidal geometry. Complex 1 shows a quasi-reversible redox response at = 0.567 V (Δ = 115 mV), while complexes 2 and 3 exhibit quasi-reversible cyclic voltammograms with values of 0.405 V (Δ = 80 mV) non-aqueous Ag/Ag. The cyclic voltammograms indicate that the formation of a Cu(II) complex from the oxidation of 1 required more anodic potential than that from the oxidation of 2, highlighting the influence of the ligand environment on redox properties. Complexes 2 and 3 are interconvertible and exhibit high superoxide dismutase (SOD) mimetic activity, efficiently dismutating O˙ to O and HO with an impressive IC value of 5.1 × 10 M. Upon electrochemical oxidation, under an N atmosphere complex 1 forms complex 4, which in the presence of air, converted to complex 6 through complete breaking of imino bonds, resulting in the formation of aldehyde and carboxylic acid in a 2 : 1 ratio. The generation of carboxylic acid implies that the transformation of 4 to 6 involves not only hydrolysis of the imino bonds but also oxidative degradation of the imino moiety or its aldehyde products. Furthermore, treatment of complex 2 with KO in the presence of protons leads to the formation of complex 8 and 1-pyrenecarboxylic acid. This transformation likely proceeds Cu(II)-hydroperoxo intermediates, which oxidize 1-pyrenecarboxaldehyde, which is itself a product of partial imine bond cleavage in complex 3. Density functional theory (DFT) calculations were conducted to rationalize and support the experimental observations and the proposed mechanistic pathways.