Study On The Structures And Properties Of Metal-Organic Frameworks(MOFs) Based On Aniline Carboxylic Acids And Benzidine Carboxylic Acids

Metal-organic framework(MOFs)is a new kind of porous crystalline material constructed by metal ions or metal clusters and organic ligands.It was widely used in many fields,such as gas storage,gas separation,heterogeneous catalysis,chemical sensing and so on for its diversity function.In this paper,we have synthesized nine kinds of MOFs,constructed by the mayor ligands triphenyltricarboxylic acid and tris((4-carboxyl)phenylduryl)amine,the neutral bridging organic ligands,and the transition metal ions.Then we have determined their crystal structures and the properties in the area such as gas adsorption,dye adsorption,fluorescence detection and catalysis.This paper contains five parts,the first part introduces some concepts about MOFs and synthesize methods,and discussed the research progress of MOFs which were constructed by tris((4-carboxyl)phenylduryl)amine ligand,tricarboxytriphenylamine ligand^as well as the development of fluorescent and porous MOFs.In the second part,we have synthesized three MOFs:[Zn2(TCA)(bib)2.5]·NO3(compound 1),[Mn3(TCA)2(bib)(DMA)2](compound 2)and[Ni2(TCA)(bib)3](compound 3),which were constructed by tricarboxytriphenylamine and 1,3-bis(imid-azole-l-ylmethyl)benzene.Compound 1 is a cationic framework,Moreover,activated 1 showed highly selective adsorption towards CO2 over N2 and CH4 under ambient conditions at 273 K.In addition,compound 1 was developed as a highly selective and sensitive probe of Fe3+ and salicylaldehyde in aqueous solutions.Compound 1 was able to detect Fe3+ under simulated physiological conditions,and we also discussed possible sensing mechanism based on cation exchange between Fe3+ and the fra1ework Zn2+ in compound 1.Moreover,compound 1 features excellent catalytic activity to the cycloaddition of CO2 to epoxides.In the third part,we have synthesized four MOFs:[Cd3(TCA)2(bbi)3(H2O)2](compound 4),[Zn3(TCA)2(bbi)](compound 5),[Mn3(TCA)2(bbi)](compound 6),[Ni3(TCA)2(bbi)3(H2O)2](compound 7),which were constructed by tricarboxytrip-henylamine and 1,4-bis(imidazol-1-yl)butane.Compound 4 also has strong fluorescence intensity,which could be used as a fluorescent probe for detection of transition metal ion(Fe3+)and salicylaldehyde in aqueous solutions.In the presence of interfering ions,compound 4 could selectively recognize Fe3+.In the forth part,we have synthesized two MOFs:[Cd3(TPA)2(bimb)3(H2O)2](compound 8),[Mn3(TPA)2(bmb)](compound 9).Compound 8 and 9 are three-dimensional network.Moreover,compound 8 has an exposed metal-unsaturated coordination site on the pore surface,and the activated compound 8 could be used as a potential material for selective separation of CO2/N2 and CO2/CH4 at 273 K.Meanwhile,compound 8 showed better dye adsorption behavior.Compound 8 could selectively adsorb anionic dyes under certain conditions,and with the increase of dye size,the adsorption effect becomes slower.In the fifth part,we make a brief summary of the research results and put forward the innovation of the paper,In addition,the prospect for the application of MOFs as a fluorescent material.