Studies On The Synthesis,Structures And Characterization Of Transition Metal Complexes With Bis(5-amion-1H-1,2,4-Triazole) And Its Derivatives

The coordinative assembly of novel framework and properties based on transition metals and triazole and its derivatives ligands attracts much attention.Compared with the triazole and its derivatives ligands,bis-1,2,4-triazole and its derivatives ligands may exhibit more various coordination modes,due to the different rotation angle of the pyridine or triazole rings,and the active hydrogen atoms of triazole rings.In this paper,we have designed a azolate ligands:Bis(5-amion-lH-1,2,4-triazole)(H2L1).As the amino with a lone pair electrons,on the one hand,can be used as a coordination atoms,on the other hand it is also a good organic intermediates.We successfully synthesized a series of transition metal complexes.And we modified amino of H2L1.We synthesized three macrocyclic ligands metal complexes and tried to explore the synthesis mechanism.We further modified amino of H2L1 to a symmetrical mide group and used it synthesized complexes.And H2L1 is used to carry out step by step amide synthesis of asymmetric amide compounds.We controlled different experiment conditions to construct novel compounds by H2L1 and its derivatives.The structures of these complexes have been determined by X-ray crystallographic methods and characterized by element analyses and IR spectra.The interaction between some of these complexes and BSA has been researched.The main work in this paper includes fuour chapters:Chapter One:We introduce the development of the coordination polymers including synthetic method and influencing factors,as well as the feature of triazole ligands and its derivatives.In addition,summary of the recent research progress on the structures of triazole ligands and its derivatives compounds.Chapter Two:Eight complexes of H2L1,namely,[Ni(H2L1)(H2O)2]·SO4·H2O(1);[Co(H2L1)(H2O)2]·SO4-H20(2);[Cu(H2L1)2(H2O)]·(NO3)2-H2O(3);[Co2Cl4(H2L1)2](4);[Mn2Cl4(H2L1)2]n(5);[Cd2Cl4(H2L1)2]n(6);[ZnCl2(H2L1)]n(7);[Mn2(HCOO)2(L1)]n(8),complexes(1)-(3)are mononuclear complexes,(1)and(2)are isomorphous.(4)is dinuclear cluster.For(5)-(7),M(Ⅱ)ions are bridged each other through μ2-Cl or μ2-H2L1 to form 1D infinite chains.And(5)and(6)are also isomorphous.In(8),Mn(II)ions are bridged each other through μ2-HCOO or μ2-H2L1 to furnish 3D structure.The interaction between(1),(2)and bovine serum albumin(BSA)under physiological conditions was investingated by UV-VIS spectra,fluorescence quenching methods and CD spectra.We obtained the quenching constants KSV,binding constants K.We further modified amino of H2L1 to synthesis novel ligands or novel complexes since coordination model of H2L1 is fixed.Chapter Three:As a result of the ligand H2L1 with a fixed mode,to better control,so we by modifying the ligand of amino substituent.And the amino substituent is good intermediates in organic synthesis.New square-planar M(Ⅱ)complexs of 18-membered octoaza macrocyclic ligands has been synthesized by template synthesis.The M(II)complex has square-planar coordination geometry and contains eight nitrogen atoms.And we tried to explore the synthesis mechanism.We synthesized the macrocyclic ligands under the hydrothermal conditions with the metal radius template and tried to explore the synthesis mechanism.It is N-alkylation of amines raction.The interaction between square-planar complexs(9)～(11)and BSA under physiological conditions was investingated by UV-VIS spectra,fluorescence quenching methods and CD spectra.We obtained the quenching constants KSV,binding constants K.Chapter Four:We also modified the amino function of H2L1 to amide.Found that it is easy to get symmetric amidation ligand so we use H2L1 as raw material to get Bis(5-acetylamino-1H-1,2,4-triazole)ligand(H2L3).Two complexes of H2L3,namely,[Ni3(HCOO)2(L3)2(H2O)2]·2H20(12);[CoⅢCOⅡI2(N3)2(L3)2(H2O)4]·N3·H2O(13).They both are trinuclear complexes.We also used H2L1 as raw materials under hydrothermal conditions successfully synthesized unilateral amino modified into amide Ni,Cu metal complexes[Ni4(S04)2(HL4)4(H20)6]·6H20(14);[Cu2(S04)(HL4)2]n(15);[Cu2C12(HL5)2]·2H2O(16).The asymmetric amide compounds can be used as a synthesis of intermediates,try to explore amide synthesis method step by step.The interaction between square-planar complexs(13)～(14)and BSA under physiological conditions was investingated by UV-VIS spectra,fluorescence quenching methods and CD spectra.We obtained the quenching constants KSV,binding constants K.And comparing with the previous complexes analysis found that the complexes of amide ligand on the effect of BSA was obvious effect.