Highly Efficient C-H Oxidative Activation by a Porous MnIII-Porphyrin Metal-Organic Framework under Mild Conditions

A simple strategy to rationally immobilize metalloporphyrin sites into porous mixed-metal-organic framework (MMOF) materials by a metalloligand approach has been developed to mimic cytochrome P450 monooxygenases in a biological system. The synthesized porous MMOF of [Zn-2(MnOH-TCPP)(DPNI)]0.5DMFEtOH5.5H(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 -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 MMOF catalyst.