Under kinetic guidance, the stable metal‐organic framework PCN‐224 was synthesized and used as the parent MOF to embed Mn³⁺ 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 (H₂L), was also designed and synthesized. The PCN‐224(Mn) was then modified by introducing the H₂L into its structure, forming a new hydrophobic porphyrinic MOF of PCN‐224(Mn)‐H₂L. The catalytic oxidation performance of PCN‐224(Mn)‐H₂L to cyclohexane was investigated. It was found that the hydrophobicity and stability of PCN‐224(Mn)‐H₂L 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.

中文翻译：

---

通过高效的后修饰将官能团结合到卟啉金属有机骨架中

在动力学指导下，合成了稳定的金属有机骨架PCN-224，并用作母体MOF嵌入Mn ³⁺形成PCN-224（Mn）。还设计并合成了具有两个羧基和含氟基团的分子，称为邻苯二甲酸2,2'-双（三氟甲基）-4,4'-联苯二酚（H ₂ L）。然后通过将H ₂ L引入其结构来修饰PCN‐224（Mn），形成PCN‐224（Mn）‐H ₂ L的新型疏水性卟啉MOF.PCN‐224（Mn）‐的催化氧化性能研究了H ₂ L为环己烷。发现PCN‐224（Mn）‐H ₂的疏水性和稳定性L显着改善，并且具有优异的催化性能，在温和的反应条件下对KA（环己酮和环己醇的混合物）的选择性为90％，环己烷转化率为51.3％，远优于PCN-224（Mn ）和均相的金属卟啉催化剂。在多次重复实验后，催化剂保持稳定。