Synthesis,Structures And Properties Of Metal Complexes With Sulfur-containing Triazole Ligand Complexes

Over the last few decades,the research of crystal engineering about the self-assembly of transition metals and triazole complexes has received a lot of chemists’ attention.Under this background,the structure of complexes,which is formed by covalent bonds,hydrogen bonds,π-π stacking or other interactions,has successively been reported.In the literature,there are many factors influencing the structure of complexes,however,there is no such a theory to explain this factors.In addition,the in-situ reaction of solvent thermal,as one of the most important methods in coordination chemistry research,has been widely applied in the synthesis of the novel complexes,the explaination of organic reactions and reaction mechanisms.There are mainly two parts in this thesis,including the advances in azole ligands and N-S-heterocyclic complexes and the research paper.The detailed explanation is as follows:Section one:We mainly aim at reasearching the advances in azole ligands and N-,S-heterocyclic complexes and the factors about affecting the structure-diversity complexes.Section two:Research papers,including the preparation of the sulfur-containing triazole ligands and complexes and the research of their structure and properties.Concrete content is as follows:1.The three azole ligands,Bis(5-mercapto-4H-1,2,4-triazol-3-yl)alkanes(L1),5-(pyridine-2-yl)-1,2-dihydro-1,2,4-triazole-3-thione(H2L2),N-picolinoylpicolinohydrazide(H2L3),have been synthesized by our group.Then,we did a study to explore their synthesis methods and various factors which affecting the yields of the ligands.Moreover,the structures of these ligands have been gained through X-ray diffraction analysis.2.Seven novel complexes were separated from the reactions of as-prepared ligands with different metal salts by solvothermal method.The molecular formula of the seven novel complexes are(1),[Cu2(L1a)2(H20)2]n,(2),[Cu2(L1b)2(H20)2]n,(3),Co(L1b)2(H2O)2],(4),[Ni2(L2)2(H2O)6]·SO4,(5),[Cu3(HL2)2L3Cl3]·H2L3,(6),[Cu3C12(L3)2H2O]and(7),[Cu2(L3)2]n·nH2O.(8)[Cu3L4(μ2-S)L5]n In the meantime,5-thione-3-carboxylic acid-1,2,4-triazole(L1a)and 3-carboxylic acid-1,2,4-triazole(L1b)were separated from the reactions of L1 with transition metals via in-situ reaction of solvent thermal.The structures of as-prepared complexes have been determined by X-ray diffraction analysis and characterized by IR spectra.Furthemore,magnetic properties and thermogravimetric analysis of some complexes have been briefly investigated.Complex(1),(2)and(3)were separated from the reactions of Li with CuCl2,CuCl,and CoCl2.6H2O by solvothermal method respectively.X-ray diffraction analysis reveals that complex(1)and(2)are formed via the coordination mode of μ3-η2:η1:η1 with Cu ions as the central ions,while complex(3)is formed via the coordination mode of μ-η2 with Co ions as the central ions.We also found that complex(1)is a two-dimensional plane structure,complex(2)is a three-dimensional structure and complex(3)is a mononuclear Co(Ⅱ)complex.Furthemore,magnetic properties and thermogravimetric analysis of the three complexes have been briefly investigated.They all exhibit antiferromagnetic interaction.Four novel complexes were separated from the reactions of H2L2 and L3 with NiCl2·6H2O and CuCl2 by solvothermal method respectively.By the coordination mode of μ2-η2-η1,complex(4),a nickel dual-core complex have been formed.Complex(5),(6)and(7)are attributed to copper complexes.Complex(5)is trinuclear complex,the two coordination modes of it are μ1-η1 and complex(6)and(7)are formed via the coordination mode of μ2-η3-η2 and μ2-η3-ηrespectively,and complex(6)is trinuclear complex while complex(7)is one-dimensional chain complex·complex(8)is trinuclear complex formed via the coordination mode of μ2-η3-η2 andμ1-η23.Based on the above studies,the influences of the electronic structures of the first series of transition metals on L1 were also investigated under solvothermal conditions.The results indicated that the Mn(Ⅱ)and Zn(Ⅱ)ions had smaller effects on L1 and did not occur the situ reactions while the Cu(Ⅱ)and Co(Ⅱ)ions had bigger effects on L1 and occured the situ reactions to generate new compounds.Furthermore,we speculated the possible mechanism of the situ reactions as well.