Lanthanide-Based Polymers with Charged Ligand Backbones: Triple-Stranded Chain Structures and their DNA Cleavage Studies

Abstract

Four rare-earth metal complexes, [Ln(Ccbp)3(H2O)3]n (Ln = La (1), Ce (2), Pr (3) and Nd (4)) are synthesised from the ligand H2CcbpBr (H2CcbpBr = 4-carboxy-1-(4-carboxybenzyl)pyridinium bromide) and the respective lanthanide metal ions. Complexes 1–4 are isostructural in that every three Ccbp– ligands juxtapose two Ln3+ ions in a monodentate coordination mode to form triple-stranded one-dimensional chain structures. Each central Ln3+ atom further associates with three H2O molecules, furnishing a monocapped square-antiprism geometry. Agarose gel electrophoresis studies indicate that 1–4 are capable of cleaving DNA in the presence of H2O2, most probably via an oxidative cleavage mechanism. Complexes 1 and 2 exhibited catalytic efficiencies (kmax/KM) of 37.69 and 34.11 h–1 mM–1, and are approx. 15- and 20-fold more effective than those of complexes 3 (kmax/KM = 1.75 h–1 mM–1) and 4 (kmax/KM = 2.21 h–1 mM–1).