| Metal-Organic Frameworks materials have received extensive attention of researchers because of their potential application prospects on magnetism,organic catalysis,photocatalytic degradeation,luminescent materials,drug releasing,gas adsorption,nonlinear optics and so on.It is crucial to select the organic ligands and metal ions in the process of synthesising complexes which have novel structures and excellent properties.The coordination modes of carboxyl and nitrogen atoms are both varied especially that a ligand contains carboxyl and nitrogen atoms at the same time.In addition,individual metal ions or metal clusters,the reaction temperature,the solvent and p H etc can all regulate the structures and properties of the products.Based on the above principles,we constructed a series of complexes under solvo(hydro)thermal conditions based on Triazole Tricarboxylic acid and Zoledronic acid which contain nitrogen and oxygen coordination sites,and then we analyzed their structures and properties.The full text mainly divides into three parts as follows:In the first chapter,we introduced the research background,the definition,organic ligands,inorganic non-metallic center,synthesis methods,properties and applications of the MOFs,and then we simply summarized the significance and the experiment results of this part.In the experimental section,we received five new compounds by 3-(3',5'-benzene dicarboxylic acid)-5-(3'-benzene carboxylic acid)-1,2,4-triazole: [Co3(L)2(H2O)6]?2H2O(1),[Mn3(L)2(H2O)6] ?2H2O(2),Mg2(HL)2(H2O)(3),[Mg(HL)(H2O)2]?2H2O(4),Ni3(L)2(H2O)12(5).Complexes 1 and 2 are isostructural and constructed by trinuclear Co3(Mn3)SBUs.Adjacent trinuclear Co3(Mn3)linked by carboxyl generates 1D chains,which were further ligated by L3-to present(4,8)-connected 3D flu topology.Both complexes 1 and 2 have degradation to methyl orange,neutral red and malachite green which show different charges.Their both have the best catalytic effects to neutral red,especially that the degradation rate to neutral red of complex 2 reached 91% within 120 min.Moreover,Complexes 1 and 2 with uncoordinated N atoms can act as Lewis base which are effective heterogeneous organocatalysts for the Knoevenagel condensation.Under the optimized condition of air atmosphere,the temperature of 60? and the solvent of DMF,the catalytic efficiency of different benzaldehyde derivatives and malononitrile reached more than 90%,and the catalytic effects was not significantly reduced after repeated 5 times.Complex 3 shows blue phosphorescent emission bands at ?ex=373 nm attributting to the ligand centered transitions perturbed by metal ions.Complex 3 exhibits highly sensitive sensing of water via quenching.In the second chapter,we gave a brief introduction to the definition of diphosphonic acid and its development firstly,and then we showed the excellent functions and the development situation of Zoledronic acid and its complexes.Lastly,we simply summarized the significance and the experiment results of this part.In the experimental section,we received four new compounds by Zoledronic acid: [Zn(H3Zol)2? H2O]?2H2O(6),Zn2(Zol)(H2O)(7),Ca(H2Zol)(H2O)(8),Zn(H3Zol)2?4H2O(9).Complex 6 shows zero dimension molecular structure and complex 7 has a 3D structure.Complexes 8 and 9 are both compounds with simple structures of 1D chain.For complexes 6 and 7,we conducted the drug releasing research by simulating fluid PBS.The half-life of complexes 6 and 7 are 29.5h and 51.2h respectively.And their releasing rates are both good and the clinical adverse reaction of the drugs due to the sudden releasing can be avoided in theory.The different half-lifes of complex 6 and complex 7 which can be attributed to the differences of the structures.Lastly,we fitted the two drug releasing models and calculated their related parameters R,T1/2,N.The results showed that the releasing kinetics are in line with the Weibull fitting and the fitting coefficients are 0.9987 and 0.9987 respectively.The third chapter simply summarized all contents of this paper. |
PDF Full Text Request