Highly Efficient CH Oxidative Activation by a Porous Mn III –Porphyrin Metal–Organic Framework under Mild Conditions

A simple strategy to rationally immobilize metalloporphyrin sites into porous mixed‐metal–organic framework (M′MOF) materials by a metalloligand approach has been developed to mimic cytochrome P450 monooxygenases in a biological system. The synthesized porous M′MOF of [Zn 2 (MnOH–TCPP)(DPNI)] ⋅ 0.5 DMF ⋅ EtOH ⋅ 5.5 H 2 O ( CZJ‐1 ; CZJ=Chemistry Department of Zhejiang University; TCPP=tetrakis(4‐carboxyphenyl)porphyrin); DPNI= N , N′ ‐di(4‐pyridyl)‐1,4,5,8‐naphthalenetetracarboxydiimide) has the type of doubly interpenetrated cubic α‐Po topology in which the basic Zn 2 (COO) 4 paddle‐wheel clusters are bridged by metalloporphyrin to form two‐dimensional sheets that are further bridged by the organic pillar linker DPNI to form a three‐dimensional porous structure. The porosity of CZJ‐1 has been established by both crystallographic studies and gas‐sorption isotherms. CZJ‐1 exhibits significantly high catalytic oxidation of cyclohexane with conversion of 94 % to the mixture of cyclohexanone (K) and cyclohexanol (A) (so‐called K–A oil) at room temperature. We also provided solid experimental evidence to verify the catalytic reaction that occurred in the pores of the M′MOF catalyst.