Four novel complexes based on the ligand piperazine (Pip) in a chair conformation have been synthesized, namely [Pd(5,5Ј-dcbpy)Pip]·4H 2 O (1), [Pt(5,5Ј-dcbpy)Pip]·3H 2 O (2), [Pd(4,4Ј-dcbpy)Pip]·4H 2 O (3), and [Pt(4,4Ј-dcbpy)Pip]·2H 2 O (4; 4,4Ј-dcbpy = 2,2Ј-bipyridyl-4,4Ј-dicarboxylate, 5,5Ј-dcbpy = 2,2Ј-bipyridyl-5,5Ј-dicarboxylate). The four complexes were characterized by elemental analysis, FTIR spectroscopy, 1 H and 13 C NMR spectroscopy, and single-crystal X-ray diffraction analysis. In addition, gel electrophoresis was per-
[a]5741 formed on the four complexes and further insight into these complexes was gained by quantum chemistry calculations. The interaction of these complexes with fish sperm DNA (FS-DNA) was studied by UV/Vis and fluorescence spectroscopy, which revealed that they have the ability to bind to FS-DNA. The IC 50 values of the four complexes range from 8.3 to 32.5 μM. Finally, we studied the cytotoxic activities of complexes 1-4 against two different cancer cell lines.devoted to the design and synthesis of new platinum anticancer drugs and their clinical trials for the cure of cancer. [2] Moreover, other transition-metal complexes, such as Pd 2+ , Ru 2+ , Ru 3+ , Fe 2+ , Co 2+ , Ni 2+ , Cu 2+ , and Zn 2+ have been designed and extensively investigated for their biological activity. [3] It is noteworthy that among transition-metal complexes of biological relevance, a broad range of parent Pd II /Pt II compounds bearing a variety of N-containing ligands have been extensively explored for their antitumor activity. Both Pd II and Pt II are soft Lewis acids and give rise to stronger bonds with nitrogen donors (soft bases) than oxygen donors (hard bases). From a kinetic and mechanistic point of view, the mechanism of action of platinum(II) anticancer drugs as well as of their palladium(II) analogues are suitable models for future drugs, because they exhibit around 10 4 -10 5 times higher activity than many related compounds; from a structural point of view, their structures and equilibrium behavior are similar. [4] As a consequence, numerous pairs of palladium and platinum complexes have been widely studied as anticancer drugs. [5] Of these, squareplanar platinum(II)/palladium(II) coordination complexes of diimine ligands have attracted considerable attention and interest due to their unique luminescent properties, [6] which may be exploited in chemosensing [7] and photocatalysis [8] as well as for their pronounced biological activity. [5a,9] Specifically, dipyridyl and its derivatives can form square-planar coordination complexes with platinum(II)/palladium(II).
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Scheme 1. Synthesis of Pt/Pd complexes 1-4.On the other hand, piperazine is a good hydrogen-bond acceptor, which is beneficial for the coordination of metal ions to form supramolecular assemblies that are interesting building blocks with chair or boat conformations. [10] It is noteworthy that piperazine shows little toxicity and, consequently, it is widely used in medicine, [11] for example, in the prepara...