Synthese,Crystal Structures And Properties Of Metal-organic Framewoks Based On 1,2,4-Triazole Carboxylic Acid

In this thesis,we used 1,2,4-triazole carboxylate liands,3,5-bis?3',5'-Dicarboxyl phenyl?-1H-1,2,4-triazole?H4L?and 3-?3,5-dicarboxylphenyl?-5-?4-carboxylphenyl?-1H-1,2,4-triazole?H₃L'?,and solvothermally synthesized 9 MOFs based on H4L and 4 MOFs based on H₃L' with alkaline earth metal Ba???,transition metal salts Zn????Cd????Cu???and lanthanide metal salts Ho????Dy????Tb????Gd???.They are shown as follows:[Zn?HL??H₂O?₂]·NH₄⁺?1?[Zn₂L?bpp?₂]·5DMA?2?[Cd₃L₂?H₂O?₂]·2?CH₃?₂NH₂+·5DMF?3?[CU6L3?H₂O?₄?HCOO?]'?CH₃?₂NH₂+-20DMF?4?[Ba₃L₂?H₂O?₂]·4?CH₃?₂NH₂+-2Cl-?5?[Ho₃L₂?H₂O?6]·?OH?₂DMF?6?[Dy₃L₂?H₂O?6]·?OH?₂DMF?7?[Tb₃L₂?H₂O?₅]·?OH?·2DMF?8?[Gd₃L₂?H₂O?₅]·?OH?·2DMF?9?[Gd₃L₃?HCOO?]·Me₂NH₂+·7DMF?10?[Tb₃L₃?HCOO?]Me₂NH₂+·7DMF?11?[Ho₃L₃?HCOO?]·Me₂NH₂+·7DMF?12?[Dy₃L₃?HCOO?]Me₂NH₂+-7DMF?13?The crystal structures of Metal-Organic Frameworks 1-13 were measured by single crystal X-ray diffraction analyses,and were characterized by elementary analysis,IR,thermogravimetric analysis and PXRD.1 crystallizes in the monoclinic C2/c space group and exhibits a?3,3?-connected 2D network..2 crystallizes in the orthorhombic Pnna space group and shows a 2D network with ID tubes of ca.0.95 x 1.26 nm.3 crystallizes in the monoclinic C2/c space group and shows an inorganic chain connected by[Cd3?COO?8]SBUs and further forms an extended 3D network linked together via L4-ligands.4 crystallizes in the tetragonal P4/mnc space group and shows a 3D supramolecular framework.5 crystallizes in the monoclinic C2/m space group and shows microporous three-dimension.At the same time,the luminescent properties of Metal-Organic Framework 1,2,3 and 5 were investigated.In comparison with that of free H4L,the emission bands of 1,2 and 3 are red-shifted,which may be assigned to the the ligand-to-metal charge-transfer,The emission bands of 5 is not changed.The adsorption performance of 4 were researched and shows good adsorption performance to different gas.Based on H4L,6-9 were synthesized.A single-crystal X-ray diffraction analysis revealed that the four MOFs are isostructural except the lanthanide ions used,and crystallize in the monoclinic crystal system,C2/m space group.The different luminescent response to small molecules of 8 were studied.Based on H₃L',10-13 were synthesized.The single-crystal X-ray diffraction analysis revealed that that the four MOFs are isostructural except the lanthanide ions used.They crystallize in the monoclinic crystal system,C2/m space group.The adsorption performance of 10 was researched.The different luminescent response to small molecules of 11 were studied.The results show that 8,11 are all have different luminescent response to different small molecules.