Biomimetic Activation of Molecular Oxygen with a Combined Metalloporphyrinic Framework and Co‐catalyst Platform

Abstract Cytochromes P450 are powerful biocatalysts that present high catalytic efficiency in the aerobic oxidation of hydrocarbons under mild conditions. Even though metal–organic frameworks (MOFs), consisting of biomimetic metalloporphyrin moieties, are highly active in a number of reactions, they are almost powerless in the aerobic oxidation of inert hydrocarbons under mild conditions. Inspired by the catalytic mechanism of enzymes, we introduce N ‐hydroxyphthalimide (NHPI) as an assistant catalyst to help metalloporphyrinic MOF catalysis, for which NHPI acts as a proton‐ and electron‐transfer mediator. The coupled biomimetic system is efficient in the aerobic oxidation of arylalkanes under mild conditions. The catalytic efficiency is significantly improved if the [WZn{Co(H 2 O)} 2 (ZnW 9 O 34 ) 2 ] 12− polyoxometalate is used as a co‐catalyst. The biomimetic platform exhibits enzyme‐like characters by imitating the structural features, active sites, and catalytic mechanism of enzymes.