Copper perchlorate catalyzed oxidative cyclisation of a novel bishydrazone ligand, formation of an unusual copper complex and in vitro biological implications

A novel hexadentate bishydrazone ligand, 1,10-bis(di(2-pyridyl)ketone) adipic acid dihydrazone (H₂L¹) is synthesized and characterized. With copper perchlorate as a catalytic oxidant, the ligand undergoes oxidative cyclisation and resulted in the formation of an unusual copper complex [Cu(L^1a)₂Cl]ClO₄ (1), where L^1a is 3-(2-pyridyl)triazolo[1,5-a]-pyridine. The Cu(II) complex was characterized physicochemically, while the molecular structure was confirmed by single crystal X- ray diffraction. In the complex cation, copper(II) is in a distorted trigonal bipyramidal coordination environment, surrounded by two triazolo nitrogen atoms and two pyridyl nitrogen atoms of L^1a and a chloride atom. The relevant non covalent intermolecular interactions of the complex quantified using Hirshfeld surface analysis reveals that the O···H/ H···O (27.2%) contacts has the highest contribution. The solution phase bandgaps of the compounds were calculated using Tauc plot, whereas the solid-state band gaps were calculated by Kubelka-Munk model. DFT studies of the compounds indicate that the theoretical calculations corroborate with the experimental data. DPPH antioxidant activity assay of the synthesized compounds showed that the proligand H₂L¹ has a lower IC₅₀ value (24.1 μM) than that of complex 1 (29.7 μM). The in vitro antibacterial activity was evaluated against Escherichia coli and Staphylococcus aureus, which revealed that complex 1 have excellent activity against E. coli, much as the standard ciprofloxacin. The cytotoxic efficacy investigation of the compounds against A549 (lung) adenocarcinoma cells suggested that H₂L¹ has more anticancer activity (IC₅₀ value of 149.08 μM) than that of complex 1(IC₅₀ value of 176.70 μM).