The Synthesis,Characterization And Performance Study Of Metalloporphyrins Frameworks Containing Imidazole Or Pyridine Groups

Metalloporphyrin Frameworks(MPFs)are a new promising functional metal-organic materials using porphyrin building blocks as linkers,which possess the both advantages of MOFs and porphyrins.The structures of MPFs are easy to be modified and have high chemical reactivity and thermal stability.So Metalloporphyrin Frameworks(MPFs)have many potential applications in gas storage/separation,sensitive materials,biomimetic chemistry,and heterogeneous catalysis etc.So far the researches on Metalloporphyrin Frameworks(MPFs)have important consequences and become one of the hotspots in material field.Our goal is to synthesize functional porphyrins containing imidazol or pyridine group,and to construct a series of MPFs using these porphyrins as linkers,and then to study their structures and properties.The main contents are as below:1.Five new free porphyrins are synthesized and characterized by mass spectra(MS),fourier transform infrared spectra(FT-IR),ultra violet-visible spectroscopy(UV-vis),1H NMR and elemental analyses(EA).The five compounds are L1:trans-(tBu-Ph)2(Im-Ph)2Por,L2:trans-(F3-ph)2(Im-Ph)2Por,L3:trans-(F5-ph)2(Im-Ph)2Por,L4:traps-(F3-Ph)2Py2Por and L5:traps-(tBu-Ph)2Py2Por,respectively.2.Eight two/three-dimensional novel porous metalloporphyrin frameworks(MPFs)are obtained through solvothermal reactions,by using the above porphyrins metallated with Fe,Co and Ni salts respectively.The eight MPFs are[Co(tBu-Ph)2(Im-Ph)2Por]·2DMF(1),[Co(F3-Ph)2(Im-Ph)2Por]·1.5DMF(2),[Fe(Me2N,F4-Ph)2(Im-Ph)2Por]F·2.5DMF(3),{[Fe(Me2N,F4-ph)2(Im-Ph)2Por]F2(CH3)2NH2}·2DMF(4),[Fe(F3-Ph)2Py2Por]C1-2DMF(5),[Co(Me2N,F2-Ph)2Py2Por].3DMF(6),[Ni(Me2N,F2-Ph)2Py2Por].3DMF(7)and[Fe(tBu-Ph)2Py2Por]Cl·2DMF(8),respectively.The framework structures are analyzed and confirmed by the experimental methods,such as single crystal diffraction,powder X-ray diffraction(PXRD),fourier transform infrared spectra(FT-IR),ultra violet-visible spectroscopy(UV-vis),thermal Gravity Analysis(TGA)and elemental analyses(EA).The compound 3 and 4 are 3D structures,the others are 2D structures.The thermal behaviors characterized by TGA display that all three materials exhibit high thermal stabilities of the frameworks.N2,H2 and CO2 gas adsorption studies are performed on the eight activated samples.Compound 1-3 have good CO2 uptake capacities;all the MPFs have a better uptake of H2 and C02.