This article describes the synthesis and functions of a porous catalytic framework based on conjugated micro- and mesoporous polymers with metalloporphyrin building blocks (FeP-CMP). FeP-CMP was newly synthesized via a Suzuki polycondensation reaction and was developed as a heterogeneous catalyst for the activation of molecular oxygen to convert sulfide to sulfoxide under ambient temperature and pressure. FeP-CMP is intriguing because the polymer skeleton itself is built from catalytic moieties and serves as built-in catalysts, bears inherent open nanometer-scale pores that are accessible for substrates, and possesses large surface areas (1270 m(2) g(-1)) that facilitate the transformation reaction. It is highly efficient with high conversion (up to 99%) and a large turnover number (TON = 97,320), is widely applicable to various sulfides covering from aromatic to alkyl and cyclic substrates, displays high selectivity (up to 99%) to form corresponding sulfoxides, and is highly chemoselective for the oxidation of a sulfide group even in the coexistence of other oxidative functionalities. Owing to the covalent linkages between catalytic sites in the frameworks, FeP-CMP can be recycled with good retention of its porous structure and allows for large-scale transformation. These unique characteristics clearly originate from the covalent porous catalytic framework structure and demonstrate the usefulness of CMPs in the exploration of built-in heterogeneous catalysts, a new potential of these materials that have thus far been reported to exhibit noteworthy gas adsorption functions.
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