New modulated pentacoordinate complexes [C 17 H 34 N 7 O 2 Cu]ClO 4 (5), [C 17 H 34 N 7 O 2 Co]ClO 4 (6), [C 17 H 34 N 7 O 2 Ni] ClO 4 (7) have been synthesized by the interaction of 1,8-dihydro-1,3,6,8,10,13 Cu(II) (2), Co(II) (3), Ni(II) (4) hexaazacyclotetradecane complexes and Hsalea N-(2-hydroxy benzyl)-2-amino-1-ethanol ligand (1). All the complexes have been characterized by infrared, electron paramagnetic resonance, 1 H and 13 C nuclear magnetic resonance (NMR), 2D correlation spectroscopy NMR and ultraviolet–visible (UV–vis) spectroscopy. In all the complexes, the metal center is encapsulated by the Hsalea ligand in a pentacoordinate environment. Conductance measurements show that the complexes are ionic in nature. UV–vis absorption titration and viscometric studies have been carried out to ascertain the interaction of complexes 5 and 6 with calf thymus DNA (CT DNA). The experimental results suggest that complex 5 binds to CT DNA through partial intercalation of the aromatic ring into the base pair of DNA while complex 6 binds to CT DNA by electrostatic mode. The intrinsic binding constants K b of complex 5 and 6 were found to be 6.8×10 −5 M −1 and 1.8×10 −4 M −1 , respectively. The binding of complexes 5 and 6 with CT DNA has also been investigated by cyclic voltammetry.