Stannoxane capping derived from chiral tridentate NNO donor ligand for nickel and copper macrocycles: Comparative binding studies of stannoxane moiety and its modulated copper complex with CTDNA

Novel stannoxane type dinuclear tin complex C₁₆H₁₃N₄O₂Sn₂Cl₇ (1) and its modulated macrocyclic complexes C₂₄H₃₆N₁₀O₃Sn₂CuCl₇] ClO₄ (2) and C₂₄H₃₄N₁₀O₂Sn₂NiCl₇] ClO₄ (3) were synthesized and characterized by elemental analysis and various spectroscopic techniques (IR, ¹H, ¹³C, ¹¹⁹Sn NMR, ESI-MS, EPR and UV-Vis). ¹¹⁹Sn NMR shows the presence of two tin metal centers in different environment. The proposed pseudo-octahedral geometry of copper in complex 2 and square pyramidal geometry of nickel in complex 3 were established by the analysis of spectroscopic data. Absorption and fluorescence spectral studies and viscosity measurements have been carried out to assess the comparative binding of dinuclear stannoxane complex 1 and its modulated copper complex 2 with calf thymus DNA. The intrinsic binding constants K_b of the complex 1 and 2 were determined as 4.4 × 10⁴ M⁻¹ and 7.5 × 10⁴ M⁻¹, respectively. Cyclic voltammetric studies have also been employed to ascertain the binding of complex 2 with CTDNA. The results suggest that the complex 2 binds to CTDNA twice in the order of magnitude compared to complex 1. Interaction studies of complex 2 with guanosine 5′-monophosphate further confirm the binding via N₇ position of guanine and phosphate moiety.