Synthesis,Characterization And Heterogeneous Photocatalytical Application Of Functional Ordered Mesoporous Polymers

In the past ten years,visible light-induced photoredox catalysis has attracted great interest and emerged as a powerful tool to trigger organic transformations.One of the major bottlenecks of this promising field is the difficulty in the recovery and reuse of the expensive catalysts.Owing to their large specific surface area,uniform and tunable mesoporous pore size and enhanced stabilities,ordered mesoporous polymers have recently received significant attention.The physical and chemical properties of ordered mesoporous polymers can be well modulated by the introduction of functional units in the synthesis process;meanwhile,it is also easy to functionalize these materials via chemical modification.These advantages make ordered mesoporous polymers serve as excellent solid platforms for heterogeneous catalysis.Nevertheless,only very limited studies have been documented on the utilization of ordered mesoporous polymers as heterogeneous catalysts,and there have been no reports on the application of ordered mesoporous polymers in heterogeneous photoredox catalysis.Accordingly,the main contents of this thesis are centred around the synthesis and characterizeation of the functional ordered mesoporous polymers,and utilization them for the heterogeneous photoredox catalysis.Accordingly,the main achievements could be divided into the following two parts:1.Synthesis,characterization and heterogeneous photoredox catalytical application of triphenylamine(TPA)functionalized ordered mesoporous polymers.A series of triphenylamine functionalized ordered mesoporous polymers(TPA-MPs)were synthesized by a “solvent evaporation induced self-assembly” method in assistance with template,using triphenylamines containing phenolic groups as the photosensitive monomers.TPA-MPs exhibit high ordered mesoporous porosities,narrow pore size distribution and high surface area,and could be applied to catalyze the cross-dehydrogenation coupling reaction between glycine derivatives and indoles.The heterogeneous catalysts show high catalytic activity(up to 92% yield),and can be reused for at least four times with no obvious decrease of activities.2.Synthesis,characterization and asymmetric photoredox catalytic application of chiral ordered mesoporous heterogeneous photocatalysts.Firstly,carbazole(CB)or benzothiadiazole(BT)functionalized ordered mesoporous polymers(CB-MP or BTMP)were synthesized by a “solvent evaporation induced self-assembly” method in assistance with template,using carbazole derivative or benzothiadiazole derivative containing phenolic groups as the photosensitive monomers,then CB-MP or BT-MP were modified with chlorosulfonic acid,finally chiral imidazolidinone and chiral proline derivative(catalyst 1 and 2)were loaded to the pores of ordered mesoporous polymers through ionic bonding cooperation,to obtain the chiral ordered mesoporous heterogeneous photocatalysts CB-1?CB-2(or BT-1?BT-2).The obtained catalysts could be applied to catalyze the asymmetric coupling reaction between phenylpropyl aldehyde and diethyl bromomalonate,CB-1 was showing moderate activity and enantioselectivity(40% yield,55% ee).This is the first example of asymmetric photocatalytic reaction that catalyzed by organic porous materials.Further research is still under way.