Highly efficient C-H oxidative activation by a porous Mn(III) -porphyrin metal-organic framework under mild...

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 [Zn2 (MnOH-TCPP)(DPNI)]⋅0.5 DMF⋅EtOH⋅5.5 H2 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 Zn2 (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.