Design,Synthesis,and Application Of Functional Porous Organic Ploymers

Because of their large surface area, low density and synthetic diversity, porous organic polymers have drawn great research interest in recent years. The main efforts in this area focus on the design and synthesis of new functionalized porous organic polymers and their applications in the fields of gas storage, heterogeneous catalysis, organic electronics and optoelectronics.The main task of this PhD thesis is to design and synthesize several conjugated microporous polymers (CMPs) and to apply them in the area of heterogeneous catalysis, carbon dioxide storage, organic electronics and optoelectronics.In Chapter Ⅰ, we describe the development of porous organic polymers and highlight recent research progress on four typical porous organic polymers and their applications.In Chapter Ⅲ, we report the design and synthesis of three new functionalized conjugated microporous polymers as heterogeneous catalysts. First, the synthesis of (R)-BINOL functionalized porous organic polymers for heterogeneous asymmetric catalysis is achieved. This is the first example of chiral conjugated microporous polymer, with BET surface area up to598m2/g. However, the enantioselectivity of the product is very low. Then, the synthesis of Pd(PPh3)2Cl2-functionalized porous organic polymers as heterogeneous catalyst for Suzuki coupling reaction is described. We also tried to synthesize phenanthroline-functionalized conjugated porous polymers, however, polymers obtained have limited surface area.In Chapter IV, the synthesis of Troger's base-functionalized porous organic polymers via dilution and doped strategies and their application in carbon dioxide adsorption have been described. Troger's-base-doped conjugated microporous polymers show significant sorption capabilities for CO2(2.46mmol/g at273K and1.13bar).In Chapter V, design and synthesis of the first conjugated microporous polymers via through-space-conjugated comprising π-stacked structures is presented. These polymers exhibit highly photoluminescence properties due to this unique structure, and lead to green emission under irradiation with UV light, which have potential applications in the area of organic electronics and optoelectronics.In Chapter VI, we present the development of an efficient protocol to the synthesis of2-aminobenzothiazoles with part-per-million of Cul (50ppm). This system had shown broad substrate scope, moderate to good yields (49-93%), and high turnover number (67000). The reaction could be, at least, scaled up to gram-scale. Primary mechanistic studies indicated that the reaction may follow an oxidative addition/reductive elimination pathway involving Cu(I)/Cu(III) intermediates.