Synthesis,Structure And Properties Of Metal MOF Complexes And Copper,Cadmium Of Terpyridine

Since terpyridine was discovered,it can form metal complexes with various metal salts.Due to the high conjugation and stability of terpyridine,and the active N atom on the rings,it is easy to coordinate with metal ions such as Cu²⁺,Co²⁺and Cd²⁺to form novel and stable complexes.The research results in this thesis provide a new way for the synthesis of metal complexes,and also provide experimental basis for the study of anti-proliferation activity of the complexes on cancer cells,expand the research to other properties,and have certain theoretical significance and application prospects.The research of this thesis mainly includes the following parts:1.According to the synthesis method in the literature,4’-phenyl-2,2’:6’,2’’-terpyridine（L⁰）was synthesized by using 2-acetylpyridine and benzaldehyde,and then the ligand L⁰ and 1,4-Naphthalene dinaphthalate were used as raw material,respectively with three different inorganic salts Cu（OAC）_2·H₂O、Co Cl_2·6H₂O and Mn SO_4·H₂O,to generate three complexes[Cu(1,4-C₁₂H₆O₄)L⁰]_n（1）,[Co(1,4-C₁₂H₆O₄)L⁰]_n（2）,[Mn(1,4-C₁₂H₆O₄)L⁰]_n（3）by hydrothermal reaction method.The crystal structures of these three complexes were determined and analyzed by X-ray single crystal diffraction.The analysis results show that the three complexes were coordination polymers with MOF structures,and they are all bridged structures,among which[Co(1,4-C₁₂H₆O₄)L⁰]_n（2）and[Mn(1,4-C₁₂H₆O₄)L⁰]_n（3）are octahedral structures with six coordination;the complex[Cu(1,4-C₁₂H₆O₄)L⁰]_n（1）was a square pyramid structure with copper center ion of five coordination.2.According to relevant literatures,4’-phenyl-2,2’:6’,2’’-terpyridine（L⁰）and functionalized cyclized terpyridine（L）were synthesized firstly.On this[Cu₂（ONO₂）₂（L⁰）₂L]（NO₃）₂（H₂O）₂（7）were obtained by hydrothermal method or organic solvent method.The composition of the complexes was determined by IR and elemental analysis.The crystal structures of 5 and 6 were also determined by single crystal diffraction.The results show that 5 and 6 belong to P-1 space group and triclinic crystal system.5 is six-coordinated with octahedral geometry and 6 is five-coordinated with tetragonal pyramid geometry.The TG-DTA and TG-DTG methods were used to study the thermal properties of 4 and 7,and the relationship between the thermal weight loss and the compound structure was analyzed.The interaction of the four compounds with DNA sequences and proteins was simulated by molecular docking.The results show that these compounds have remarkable binding effect with macromolecules.In terms of antiproliferative activity,the IC₅₀ concentration of four complexes on A549,HCT-8 and MCF-7 cancer cell lines was determined by CCK-8 method.The experimental results showed that the antiproliferative effect of the four complexes on cancer cell lines was significantly better than that of cisplatin,which had good antiproliferative activity and was expected to become a candidate drug for anticancer drugs.3.With the raw materials of cadmium salt and4’-（p-hydroxyphenyl）-2,2’:6’,2’’-terpyridine（L¹）,4’-（p-methylsulfonylphenyl）-2,2’:6’,2’’-terpyridine（L²）,4’-（m-hydroxyphenyl）-2,2’:6’,2’’-terpyridine（L³）and4’-（p-phenylphenyl）-2,2’:6’,2’’-terpyridine（L⁴）,four terpyridine-cadmium complexes[Cd（NO₃）₂L¹]（8）,[Cd（NO₃）₂L²]（9）,[Cd（NO₃）₂L³]（10）,[Cd（NO₃）₂L⁴]（11）were synthesized respectively.Their structures were determined and analysed by X-ray single crystal diffraction and NMR.The results show that 8 and 11 are six-coordinated distorted octahedral structures,9is eight-coordinated distorted dodecahedron structures and 10 is seven-coordinated with a pentagonal bipyramidal geometry.By studying the luminescence properties of the complexes 8,9 and 11,it was found that they all exhibit respective fluorescent peaks,and the position of the substituent has a great influence on the fluorescent properties of the compounds.