The Synthesis,Properties And Theoretical Calculation On Transition Metal Complexes Of Terpyridine Halogen Derivatiives And Macrocyclic Compounds

Terpyridines and polyaza macrocyclic compounds are both multidentate ligands with strong coordination abilities to transition metal ions and their metal complexes can be used in the fields of photoluminescence,ion recognition,catalysis and biomedicine,etc.These properties have been simulated by density functional theory(DFT)calculation in recent years,which is of great significance for the design,synthesis and study of mechanism of metal complexes.In this dissertation,five terpipyridine and six macrocyclic compounds were synthesized.Reactions between these ligands and metal salts(nickel,zinc,palladium,silver)led to the formation of a series of metal complexes,which were characterized by related instruments.The single crystals of 20 compounds were determined.The photoluminescence,thermal analysis,biological activity and DFT calculation of some compounds were also studied The main contents and research results are listed as follows1.4'-(4-phenyl)-2,2':6',2"-terpyridine(L1-1),4'-(4-fluoro-phenyl)-2,2':6',2"terpyridine(L1-2),4'-(4-chloro-phenyl)-2,2':6',2"-terpyridine(L1-3),4'-(4-bromo phenyl)-2,2':6',2"-terpyridine(L1-4)and 4'-(4-iodo-phenyl)-2,2':6',2"-terpyridine(L1-5)were synthesized,which were characterized by IR,1H NMR,13C NMR and elemental analysis.The UV absorption and photoluminescence of these ligands were also studied.The structure of L1-5 was determined by single crystal X-ray diffraction.The results show that the peaks of UV absorption and fluorescence emission of these compounds display slightly redshifted or blueshifted behaviours when the H atom at the phenyl of terpipyridine are substituted by F,Cl,Br or I atoms.The charge transfers of UV absorption and fluorescent emission are assigned to internal ligand charge transfer(ILCT)2.A series of metal complexes were obtained by the reactions of terpipyridines and zinc or silver salts.These complexes were characterized by IR,'H NMR,UV absorption and crystal structure.The photoluminescent properties and biological activities of some complexes were also studied.The results show that the complexes obtained by the reactions of zinc halides,zinc nitrate or silver hexafluoroantimonate and terpyridines led to the formation of the complexes with an irregular trigonal bipyramidal,octahedral of sandwich and planar quadrilateral coordination geometry,respectively.Intermolecular ?-?interactions present in all these complexes.While hydrogen bonds and ?-ring interactions exist in some complexes.The UV absorption and fluorescence in DMSO solution show that the change of the substituents at the phenyl ring of terpyridines has a great influence on the UV absorption wavelength and fluorescence emission intensity of some complexes,with a certain regularity.The properties of zinc bromide and zinc iodide complexes show that their fluorescent emission in the solid state are related to the types of the ligands and zinc salt.Each complex presents good antiproliferative activity against A549,Bel-7402 and MCF-7 cell lines.Compared with that of cisplatin,a widely used antitumor drug,much low half maximal inhibitory concentration(IC50)against the three cell lines are observed for these complexes.These complexes can bind selectively to the active domain of the target protein kinase and the binding mode of the compounds to the proteins is Van der Waals force.3.The terpyridyl ligands and some of their zinc complexes were studied by DFT method and their structural optimization,NMR,absorption and emission spectra were calculated via different functionals.The orbital energy and the modes of charge transfer were also analyzed.The results show that B3LYP functional is suitable for structural optimization calculation of the terpyridyl ligands and PBEIPBE functional is appropriate for structural optimization of the zinc complexes.The 1H N-MR of L1-5 was calculated by B3LYP functional and the calculated value is near to the experimental value.The CAM-B3LYP functional has a relatively superior advantage in the calculation of 13C NMR for L1-5.The calculations of absorption spectra for the terpyridyl ligands show that B3PW91 is a proper functional and the charge transfer is assigned as ILCT.PBE1PBE functional is suitable for the absorption spectra calculation of Zinc halide complexes,the calculated values are near to the experimental values,and the charge transfer is assigned as ILCT or ligand to ligand charge transfer(LLCT).The calculations of emission spectra for the terpipyridines show that the 03LYP is a suitable functional for emission in high energy region and B3PW91 is a appropriate functional for the emission in low energy region.The charge transfers for both emissions are assigned as ILCT.The DFT calculation of zinc bromide and zinc iodide complexes show that the highest occupied molecular orbital(HOMO)orbital energy is primarily affected by the Zn(?)salts.The calculated values of band gaps,Gibbs free energies,electronegativity and contribution of charge transfer amount are consistent with the experimental results4.Two macrocyclic compounds(L2-1 and L2-2)were synthesised Reactions between L2-1 and several Zn(II)salts led to the formation of seven binuclear zinc complexes.A binuclear silver complex was obtained by the reaction of L2-2 and AgSO3CF3.Some of these complexes were characterized by IR,1H NMR and crystal structure.The photoluminescence and thermal analysis of some complexes were also studied.The results show that the two macrocyclic ligands are a convenient coordination source for the facile synthesis of different kinds of complexes with interesting structures.The properties of L2-1 and its zinc complexes are distinctive with the variation of the anionic auxiliary ligands.The UV absorption wavelengths of sulfonate and acetate complexes in DMF and DMSO are almost unchanged.With the hydroxyl substituent at the ortho-,meta-and para-position in benzoate complexes,the peaks of absorption wavelengths display blueshifted behaviours.The photoluminescent properties show that the emission of the sulfonate complex is significantly red-shifted relative to the ligand,and the emission of the benzoate complex depends on the position of the hydroxy at the phenyl group.All these fluorescent emission can be assigned as ILCT.The study on fluorescent quantum yields(?)show that the ? values undergo a greatly reduction when the H atom at the ortho-,meta-and para-position of phenyl are substitued by hydroxyl.TG-DTA studies show that acetate and benzoate complexes exhibit the best thermal stability,and the final stable temperature of the benzoate complexes are reduced with hydroxy substitution.5.Four kinds of functionalized macrocyclic ligands(L3-1,L3-2,L3-3 and L3-4)were synthesised.Reactions between these ligands and some metal salts led to the formation of several complexes.Some of these complexes were characterized by IR,1H NMR and crystal structure.The photoluminescence,thermal analysis and biological activity of some complexes were also studied.The results show that acrylonitrile is easy to react with different types of the macrocyclic compounds for functionalization.They can coordinate to metal salts to obtain mononuclear or binuclear complexes.Anionic ancillary ligands have an important influence on the structure,thermal decomposition,fluorescent emission and biological activity of the silver complexes which are obtained from the reaction of L3-1 and silver salts.The anti-tumor cells activity assay in vitro show that these complexes have good inhibitory activity against A549,Bel-7402 and HCT-8 tumor cell lines and their IC50 values are near to cisplatin.Other biological activity studies show that the complex which formed by the reaction of L3-1 and AgNO3 exhibits the maximum inhibition rate(100%)and the best clearance rate(9.84%)in comparison with other complexes when tested the inhibition of tyrosine kinase and radical-scavenging activity in vitro.The complex which formed by the reaction of L3-1 and AgSO3CF3 has the best protection activity against human umbilical vein endothelial cells(HUVEC)oxidative damage induced by H2O2.The complexes obtained by the reaction of L3-4 and palladium chloride,zinc chloride and nickel nitrate indicate that metal ions play a key role in the coordination reaction.It is indicative that a series of unique structures of macrocyclic compound and macrocyclic complexes could be synthesised by selecting different kinds of transition metal ions and appropriate reaction conditions.