Synthesis, Crystal Structure, Supramolecular Assembly And DNA Binding Studies Of Complexes Containing C, N, And O Coordination Atoms

In order to explore structural information and biological function of DNA and to obtain the new effective chemical druggery, a series of complexes containing C, N, and O coordination atoms has been synthesized under the solvothermal conditions or in the solution at room temperature. The complexes are composed of transition metals as the cores and phenanthroline as the principal ligand. Their structures are characterized by elemental analysis and single-crystal X-ray diffraction, and supramolecular assemblies are researched. The interactions of complexes with CT-DNA are studied using absorption and fluorescence spectrum titration measurements. The main results are as follow:1. Sixteen complexes [Cu(phen)₂]ClO4 (1),[Zn(phen)₂(H2O)Cl]Cl·1.5H2O (2),[Zn(phen)₃](ClO4)₂·H2O·CH3OH (3),[Cu(sal)(phen)ClO4]2 (4),[Cu(o-van)(phen)ClO4]2 (5),[Mn(sal)(phen)₂]ClO4 (6),[Ni(sal)(phen)₂]NO3·3H2O (7),[Pb(Hsal)₂(phen)]n (8),[Cu6(CN)6(phen)4]n (9),[Cu3(CN)₃(phen)₃]n (10),Co(NCS)₂(phen)₂ (11),Mn(NCS)₂(phen)₂ (12),[Ni(phen)₃][Ni(CN)4]·3H2O (13),{Co(phen)₂[Fe(CN)4(phen)]2}·4H2O (14),[Cu2(sal)₂(phen)₂(DMF)](HgI3)₂ (15) and [Ba(phen)₃(H2O)][Fe(CN)5NO]·1.5phen·2H2O (16) have been synthesized successfully, and their single crystals obtained. Thirteen of them have not been reported up to now.2. The results show that complexes from 4 to 16 are composed of the mixture ligands. There exist interactions not only between metal ions and ligands, but also among the different ligands, which makes the complexes more stable and more selective.3. The two metal centers of Ni/Ni, multiclear of Co-Fe-Co, binuclear of 2Cu/2Hg, and polynuclear of Ba-Fe are found in the complexes from 13 to 16. The research on these metal systems are very important to the biological system. 4. TheÏ€-Ï€stacking mode of phenanthroline is firstly constructed, and more than thirty modes are observed and discussed in detailed.5. Abundant hydrogen bonds including C-H…O,O-H…O,O-H…Cl,O-H…N,C-H…N,O-H…N bonds and S···πweak interaction are found in complexes.6. Electronic absorption spectrum titration studies of the interaction between complexes with DNA show the groove binding mode for 2 and 10, the cooperative modes of electrostatic and intercalative binding for 15, and the typical intercalative binding modes with middle-intensity for other complexes.7. All the complexes can interact with DNA, and the interactions are influenced by the metal ions (the type, coordination environment and the coordination number), ligands (the type and the number), the assembly modes and other factors. The results reveal that most of the complexes are good intercalaters to DNA, which is important for designing of antitumor drugs and antivirus drugs.