Based On The Synthesis, Characterization And Performance Of Metal-organic Framework Complexes Of Imidazole-based Porphyrin

Metal organic frameworks are composed of metal ions or metal clusters(nodes)and organic ligands through self-assembly method forming 2D or 3D net structures,which have been widely applied in gas adsorptions,selective catalysis,fluorescence and other fields.MOFs with porphyrinc ligands as building units have a wide range of applications such as catalysis,sensing,optical absorption.In the second chapter,we synthesized complexes 1 and 2 by reactingNi(?)or Cu(?)with meso-tetra(4-imidazoyl)porphyrin(TIMP).Results show that compounds 1 and 2 are isomorphic in structure and they are simple metal complexes,and the metal ions are located within the center of the porphyrin ligand.By changing the volume ratio of DMF/H2O,a 2D layered structure of complex 3 has been synthesized by reaction of Ni(?)with TImP.2D copper(?)complex 4 was obtained by heating Cu(?)and TImP(2)in DMF/H2O for 3 days.In Complex 4,the Cu(?)is in a CuN6 coordination mode,TImP uses its porphyrin center and two para imidazole groups to coordinate with Cu(?),forming a 2D network structure.The void volume of 4 is 13.9%,as estimated by PLATON.Results also show that 2 and 4 can be converted to NJNU-1.In the third chapter,solvothermal method was used to synthesize complex 5 by employing biphenyl-4,4-dicarboxylic acid,TImP and Ni(?).Results show that two kinds of Ni(?)exists in 5;Nil are located within the center of the porphyrin ligand;Ni2 is hexa-coordinated and coordinates to four imidazolyl groups of adjacent TImP ligands and two oxygen atoms of terephthalic acid.Adjacent porphyrins are intercoordinated via the Ni2 nodes into a 2D square-wave assembly.Complex 5 demonstrates ultrahigh chemical stability and good thermal stability.Complex 5 can be stable in the open air for 3 days and saturated NaOH solutions for 3 days(20?,?27.5 M).Under similar conditions,we select the metal of Ni and Cu-TImP and BPDA to synthesize complex 6.Results show that Cul is five-coordinated and coordinates to the center of the porphyrin ligand and one oxygen atoms of DMA.The fourth chapter,we used the metal of Zn(?),meso-tetra(4-imidazoyl)porphyrin(TImP)and 1,3,5-Benzenetricarboxylic acid(H3BTC),and obtained complexes 7 by using solvothermal method.Results show that two kinds of zinc(?)exists in 7;Znl locates within the center of the porphyrin ligand;Zn2 is hexa-coordinated and coordinates to four imidazolyl groups of adjacent TImP ligands and two oxygen atoms of BTC.Adjacent TImP ligands interconnected by coordinating to Zn2,forming a 1D channel with the diameter of 1.7 nm.These channels were interlinked by BTC linkers.Nil atoms were on the walls of these channels.The void volumes of 7 is 58.0%as estimated by PLATON.It has a great significance to the study of porphyrinc MOFs.We can control the coordination of imidazole groups of TImP ligand by changing volume ratio of DMF/H2O.By selecting appropriate sizes of the ligands,we are able to synthesize MOFs with better performance.