Fluorinated Porous Conjugated Polyporphyrins through Direct C−H Arylation Polycondensation: Preparation, Porosity, and Use as Heterogeneous Catalysts for Baeyer–Villiger Oxidation

Graphical Removed from the mix : The synthesis of fluorinated iron–porphyrin conjugated porous polymers through direct C−H arylation polymerization is described (see scheme). The application of these polymers as heterogeneous catalysts for Baeyer–Villiger oxidation is also discussed. By considering the high reactivity of fluorinated iron–porphyrin and good stability of porphyrin-based porous polymers, fluorinated iron–porphyrin conjugated porous polymers ( FPOP-3 – 6 ) were synthesized through direct C−H arylation polymerization. The obtained materials are chemically and thermally stable, of which FPOP-3 exhibits the highest Brunauer–Emmett–Teller specific surface area (about 840 m 2 g −1 ). For functional studies of the obtained polymers as heterogeneous catalysts, catalytic transformation of cycloketones into lactones by oxygen through Baeyer–Villiger oxidation was used as a model reaction. Fluorinated phenyl substituents of the iron–porphyrin not only are beneficial to the conversion, but also can stabilize the porphyrin to resist catalyst breakdown. The polymer FPOP-3 , with high porosity, exhibits the best catalytic efficiency and recycling effect. The recovered catalyst also shows good catalytic activities after recycling three times with a small loss in yield.