Complexes [Zn(pbm)(5-hip)₃] (1), [Zn(pbm)(5-nip)₃] (2), [Mn(pbm)(H₃btc)₂(H₂O)] (3) and [Mn(pbm)(5-nip)₃] (4), where H₂HIPA = 5-hydroxyisophthalic acid, H₂nip = 5-nitroisophthalic acid, H₃btc = trimesic acid and pbm (pyridine benzene chelate material) = 2-(2-pyridyl)benzimidazole, were identified via single-crystal XRD analyses. 1, 2 and 4 pertain to the monoclinic space group C2/c, while 3 belongs to the triclinic space group P. The interplay of CT-DNA with those complexes was delineated using ultraviolet, fluorescence, and circular dichroism (CD) spectroscopy and viscosity measurements. Complexes 1, 2, 3 and 4 interact with CT-DNA in an electrostatic or grooving mode. We wish to offer a theory-wise foundation for developing anti-tumor medicines.