Abstract
Four cyclometalated Ir(iii) complexes based on 4'-p-N,N-bis(2-hydroxyethyl)benzyl-2,2':6',2''-terpyridine (TPYOH) and 4'-p-N,N-bis(2-hydroxyethyl)benzyl-6'-benzyl-2,2'-bipyridine (PhbpyOH) were synthesized and characterized. All the Ir(iii) complexes exhibited strong MLCT absorption peaks at about 450 nm, broad emission bands in the range of 500-700 nm. Z-scan results revealed that only complex Ir1A could exhibit certain two-photon absorption with maximal cross section values of 215 GM at 890 nm. When excited by 700-850 nm femtosecond laser, complex Ir1A gave a TPEF peak around 567 nm. All four complexes exhibited enhanced cell growth inhibitory activity against MCF-7 tumour cells under light irradiation comparing to their dark toxicity, with Ir1B showing the highest PI value (>50). The pathways and efficiencies of ROS generation by Ir(iii) complexes varied, with Ir2A being more effective in producing (1)O(2) while Ir1A mainly generating O(2)˙(-). The Ir(iii) complexes undergo hydrogen bonding with DNA bases/phosphodiester through two O-H bonds on the bis(hydroxyethyl)amino group. The free pyridine-N atom in Ir1A forms additional hydrogen bond with DNA base, while the ligand TPYOH in Ir2A has better molecular planarity due to adopting {N, N, N} coordination mode, thus these two complexes show better DNA affinity. The complexes demonstrated weak interactions with BSA, through hydrogen bonding with amino acid residues at different regions of BSA molecule.