Synthesis and spectral characterization of 14- and 16-membered tetraazamacrocyclic Schiff base ligands and their transition metal complexes and a comparative study of interaction of calf thymus DNA with copper(II) complexes.

14 and 16 membered Schiff base macrocyclic ligands, 7,14-dimethyl-5,12-di(N-amino)-2-methylphenyl-1,4,8,11-tetraaza-cyclotetradecane-4,7,11,14-tetraene (L(1)) and 8,16-dimethyl-6,14-di(N-amino)-2-methylphenyl-1,5,9,13-tetraaza-cyclohexadecane-5,8,13,16-tetraene (L(2)) were synthesized by condensation reaction between 2'-methyleacetoacetanilide and aliphatic diamines. The metal complexes of the types, ML(1)(2) and [ML(2)(NO(3))(2)] [M = Co(II), Ni(II), Cu(II) and Zn(II)] were prepared by interaction of ligands, L(1) or L(2) with hydrated metal(II) nitrates. The ligands and their complexes were characterized by elemental analysis, IR, (1)H and (13)C NMR, EPR, UV-Vis spectroscopy, magnetic susceptibility, conductivity measurements and ESI-mass spectral studies. The results of elemental analyses, ESI-mass and conductivity measurements confirmed the stoichiometry of ligands and their complexes while the characteristic absorption bands and resonance peaks in IR and NMR spectra confirmed the formation of ligand frameworks around the metal ions. The square planar geometry for complexes derived from ligand L(1) and octahedral environment for complexes derived from ligand L(2) with distortion in Cu(II) complex have been confirmed on the basis of results of electronic and electron spin resonance spectral studies and magnetic moment measurements. Absorption and fluorescence spectral studies revealed different binding mode for complex, CuL(1)(2) as compared with [CuL(2)(NO(3))(2)] on interaction with calf thymus DNA.