The Synthesis, Characterization And Properties Of Porphyrin-based Metal-Organic-Gel And Porphyrin Complexes

In recent years, environment governance issues become a hot issue in modern society, the porous materials which can be used in the adsorption and transformation of pollutants have attracted widespread attention. According to the associated reports, porous materials mostly include Metal-organic-frameworks?MOFs?, Metal-organic-aerogels?MOAs? and coordination polymers?PCPs?, which regard organic ligands as building units, metal ions as nodes, while have the characteristic of organic ligands and inorganic salts. Thererore, they have pleasant prospect of application in gas adsorption, molecular recognition, heterogeneous catalysis and so on.In this article, we use the meso-substituted carboxylphenyl porphyrin as the building blocks to synthesie of five kinds of metal porphyrin complexes, and used free porphyrin and metal porphyrin as the gelator, constructed six Metal-organic-aerogels?MOAs? and twelve porous coordination polymers?PCPs?.Then we studied the potential applications in the fields of gas adsorption, luminescent materials and catalysis.Main contents are:Firstly, we designed and synthesized four free porphyrins and five metal porphyrin complexes, named 5,10,15,20-Tetra?3-aminophenyl? porphyrin ?TAPp?,5,10,15,20-Tetra ?4-propoxycarboxyphenyl?porphyrin?H₂TCPOPp?,5,15-di?4-propoxycarbomethoxy?-10,20-diphenylporphyrin?H₂Pp1?,5,15-di?4-propoxycarboxyphenyl?-10,20-diphenylporphyrin ?H₂Pp2? and corresponding ?Cu????Zn????Co????Mn????Fe???? metalloporphyrins of H₂TCPOPp. All the synthesized compounds were characterized by mass spectra ?MS?,'H NMR, elemental analyses ?EA?, ultra violet-visible ?UV-vis?, foruier transform infrared ?FT-IR? to confirm the structure.Secondly, we used H₂TCPOPp as the gelator, reacted with Al?NO3?3·9H₂O, Cr?NO3?3·9H₂O, and Fe?N03?3·9H₂O in solvothermal constructed MOG1, MOG2 and MOG3, and used Zn?TCPOPp? as the gelator instead, formed MOG4, MOG5 and MOG6. In order to fabricate metal-organic aerogel with stable mesoporous structure, we dry the porphyrin hydrogel under the supercritical conditions of CO2, obtaining the corresponding aerogel MOA1-MOA6. The aerogel were characterized by SEM, TEM, FT-IR and EA, N2 absorption-desorption indicated that they have porous structures and a larger BET specific surface areas. Then the morphology and pore structure were got by SEM and TEM. At last, we use MOAs as heterogeneous catalysts and adsorbent to study their catalytic activity and adsorptive property.Thirdly, we used H₂TCPOPp as building units reacted with ?Cu????Zn????Co???? Mn????Fe???? Ni???? respectively formed six porous coordination polymers ?CP₁-CP₆?. The coordination polymers were characterized by SEM, TEM, FT-IR and EA, N2 absorption-desorption indicated that they have porous structures and a larger BET specific surface areas. Then the morphology and pore structure were got by SEM and TEM. At last, we use MOAs as heterogeneous catalysts and adsorbent to study their catalytic activity and adsorptive property.In the end, we used H₂TCPOPp and Zn?TCPOPp? as building units reacted with Dy????Eu??? and Gd??? respectively formed six porous coordination polymers ?CP7-CP₁2?. The coordination polymers were characterized by SEM, PXRD and fluorescence.