Synthesis, crystal structure and photo-induced DNA cleavage activity of ternary copper(II) complexes of NSO-donor Schiff bases and NN-donor heterocyclic ligands

摘要

ew ternary copper(II) complexes $[CuL^{n}B](ClO_{4})(1-3)$, where $HL^{n}$ is the NSO donor Schiff base derived from the condensation of 2-mercaptoethylamine hydrochloride with salicylaldehyde $(HL^{1})$ or 2-hydroxy-3-methoxybenzaldehyde $(HL^{2})$ and B is NN-donor heterocyclic base like 2,2'-bipyridine (bpy, 1), 1,10-phenanthroline (phen, 2) or 2,9-dimethyl-1,10-phenanthroline (dmp, 3), are prepared, structurally characterized by X-ray crystallography and their DNA cleavage activity studied. The complexes show distorted square-pyramidal $(4 + 1)CuN_{3}OS$ coordination geometry in which the NSO-donor Schiff base is bonded at the basal plane and the NN-donor heterocyclic base displays axial-equatorial mode of bonding [Cu-S distance: 2.4 ]. The one-electron paramagnetic $(mu_{eff} = 1.9 mu_{B})$ complexes display axial EPR spectra in DMF glass at 77 K giving g = 2.2 (A = 162 G) and g = 2.0, indicating ${d_{x}2_{-y}2}^1$ ground state. The complexes exhibit visible spectral d-d band in MeCN near 650 nm and two charge transfer bands near 400 nm. Complexes 1 and 2 display quasireversible cyclic voltammetric response in DMF-Tris buffer (1:4 v/v, pH 7.2) for the Cu(II)/Cu(I) couple at ca. -0.1 V vs. SCE. Complex 3 exhibits an irreversible reduction process forming $[Cu^{I}(dmp)_{2}]^+$. Binding of 1-3 to calf thymus DNA shows the relative order: 2 (phen) 3 (dmp) > 1 (bpy). Complex 2 efficiently cleaves supercoiled pUC19 DNA in the presence of mercaptopropionic acid (MPA) forming hydroxyl radical or on irradiation with light of 312, 532 and 632.8 nm wavelength in a type-II process. Complexes 1 and 3 are cleavage inactive.