Incorporation of Functional Groups in Porphyrinic Metal‐Organic Frameworks by Post‐modification for Highly Efficient Oxidation Catalysis

Abstract Under kinetic guidance, the stable metal‐organic framework PCN‐224 was synthesized and used as the parent MOF to embed Mn 3+ to form PCN‐224(Mn). A molecule with two‐linked carboxyl groups and fluorine‐containing groups, which named 2,2′‐bis(trifluoromethyl)‐4,4′‐diphenyl phthalate (H 2 L), was also designed and synthesized. The PCN‐224(Mn) was then modified by introducing the H 2 L into its structure, forming a new hydrophobic porphyrinic MOF of PCN‐224(Mn)‐H 2 L. The catalytic oxidation performance of PCN‐224(Mn)‐H 2 L to cyclohexane was investigated. It was found that the hydrophobicity and stability of PCN‐224(Mn)‐H 2 L was improved markedly, and it had excellent catalytic performance with a selectivity to KA (mixture of cyclohexanone and cyclohexanol) of 90 %, a cyclohexane conversion rate of 51.3 % under mild reaction conditions, which far superior to that of PCN‐224(Mn) and the homogeneous metalloporphyrin catalysts. The catalyst remained stable after several repeated experiments.