Here, we have reported three novel copper(II) complexes (1–3) involving azo Schiff base ligands. All the complexes have been well characterized using different spectroscopic tools and single crystal X-ray diffraction analysis. Structural and electronic parameters of the complexes have been justified by DFT and TDDFT computation. All the complexes showed minor groove binding to the AT-rich sequence of DNA. The binding properties of the complexes have been extensively studied, and are further supported by a molecular docking analysis. These complexes also showed H2O2-mediated DNA cleavage properties involving a hydroxyl radical. MTT assay of the complexes was performed and they were found to be cytotoxic. The intrinsic binding constants (Kb) were calculated to be 7.11 × 105 M−1, 8.36 × 105 M−1 and 10.81 × 105 M−1 for complexes 1–3, respectively. The complexes show interesting supramolecular architectures in the solid state mainly supported by π–π stacking interactions.
