Experimental and theoretical investigation of cyclometalated phenylpyridine iridium(iii) complex based on flavonol and ibuprofen ligands as potent antioxidant

An Ir(iii) complex was synthesized using mixed ligands of biological importance, namely ibuprofen, flavonol and 2-phenylpyridine. The compound was characterized by (1)H-NMR, (13)C-NMR and TOF-MS spectroscopies and elemental analysis. Structures of the complex and its ligands were also calculated by density functional theory using B3LYP/Lanl2dz//6-31G(d) level of theory. Analyses of electrostatic potential, natural population, and frontier orbitals of the molecules as well as the calculation of intrinsic thermochemical properties such as bond dissociation enthalpy, ionization potential, electron affinity and proton affinity in the gas phase and in solvents (water and pentylethanoate) give the first indication that the complex is a potential antioxidant. The latter even shows better antioxidant capacity than the parent ligands. The antioxidant properties of the complex and its ligands were experimentally evaluated by studying the free radical scavenging activity towards HO˙, NO˙, DPPH˙ and ABTS˙(+) radicals. Further computational work on the antioxidant processes such as the single electron transfer, the proton loss, the formal hydrogen transfer (FHT) and the radical adduct formation reactions was conducted. Results show that the FHT reaction is the mechanism responsible for the radical scavenging activity of the complex towards HO˙, HOO˙, NO˙ and DPPH˙ radicals while ABTS˙(+) seems to be scavenged by an electron-donating mechanism. The FHT was further determined as a hydrogen-atom transfer but not a proton-couple electron transfer mechanism.