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

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 m2  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.