Study On Synthesis And Characteristics Of Porous Organic Networks Materials

Over the past few decades, the reserch of porous organic networks has developed rapidly. It includes a variety of categories, such as crystalline covalent organic frameworks(COFs) and non-crystalline microporous/porous organic polymers(POPs). Different types of POPs have been denoted by many different names, including polymer of intrinsic microporosity(PIMs), conjugated microporous polymers(CMPs) and hyper-crosslinked polymers(HCPs), They feature intrinsic microporous or mesoporous structures,high surface area and the well de?ned pore structure. They exhibit enormous potential applications in energy, chemicals absorption and separation, photovoltaics, gas storage, heterogeneous catalysis, biochemical sensing and so on. This thesis reports three kinds of porous organic networks, and due to their wide range of potential applications in gas adsorption and separation, sensing, heterogeneous chiral catalysis and other different fields. It shows the wide application value of the porous organic networks in different fields.Based on the effective utilization of resources to maximize and the concept of sustainable development, to combine a variety of performance on one material become a hot topic gradually. In chapter three. We report a multifunctional carbazole-based conjugated microporous polymer MFCMP-1. It is successfully prepared by oxidative coupling polymerization using a single monomer and structurally characterized. New three-dimensional π-conjugated polymer framework can be combined permanent microporous, highly luminescent properties and abundant nitrogen activated sites in skeleton. MFCMP-1 features a high concentration of Lewis base nitrogen sites on its internal surfaces; it acts good selectivity towards CO2 over N2 and CH4; works as a luminescent chemosensor towards hazardous and explosive molecules, and exhibits a highly efficient recyclable heterogeneous organocatalyst towards Knoevenagel reaction. Furthermore, we further highlight that the ease of synthesis and low cost, coupled with multifunctional properties, make MFCMP-1 an attractive functional material in practical application.In chapter four, by changing the binaphthol 3, 3’ positions of the substituents, we designed and synthesized a new class of chiral binaphthol phosphoric acid. Based hyper-crosslinked polymers are synthesized successfully using chiral binaphthol phosphoric acid as building blocks. We have synthesized a new chiral hyper-crosslinked polymers(BNNPA-HCPs). BNPPA-HCPs derived heterogeneous catalyst with high permanent surface area, good stability and chiral catalytic centers on the skeletons, which is highly active and selective in asymmetric hydrogenation organocatalysis, for the asymmetric hydrogenation of benzoxazines, benzoxazinones or quniolines derivatives. The resulting networks were found to be excellent recyclable heterogeneous catalysts for the asymmetric hydrogenation. Moreover, new strategy showed a wide adaptability and many kinds of homogeneous-like solid based catalysts with high catalytic performance and excellent recyclability can still be constructed. Application of HCPs is still limited to gas adsorption and separation, our work expanded the scope and value in practical application greatly.Intracellular pH plays a key role in physiological and paththological processes, such as enzymatic activity, inflammation and tumor growth. As minor pH variations may induce celluar dysfunction, quantitatively detecting proton is of great importance in cellular analysis or diagnosis. Fluorescent probe gradually become the research focus of porous organic materials. Covalent organic frameworks fluorescent probe for pH value reported of the literature barely. In chapter five. Condensation of triformylphloroglucinol with 2, 5-dimethoxyterephthalohydrazide under solvothermal conditions based on combined reversible and irreversible organic reactions yields crystalline two-dimensional covalent organic frameworks. The new COF(COF-JLU4) shows the expected keto-enamine form, permanent porosity with high surface area and highly chemical stability toward organic solvents, water, acidic and basic media. The fluorescent properties of COF-JLU4 are influence strongly by pH value of the medias with an extensive ranging from 1 to 13. The crystalline and the skeletal structure of COF-JLU4 haven’t been change. This report indicates that the COF-JLU4 can potentially be applied in fluorescent pH sensing. To the best of our knowledge, this study is the first example of applying COFs materials as pH sensor.