Site Isolation of Catalytically Active Mn(III)-Porphyrin into Porous Materials

Abstract

Porous materials (PMs) including porous coordination polymers (PCPs), metal–organic frameworks (MOFs), porous organic polymers (POPs), and polymers with intrinsic microporosity (PIMs), have received much attention and they often show novel and/or enhanced performances in wide range of applications such as catalysis, separation, gas storage, drug delivery, biosensing, and imaging. Although they can be successfully obtained by controlling the growth conditions, their fabrication is still a major challenge because of lack of information regarding the crucial factors for the precise control of particles during the synthesis. Furthermore, the translation of building blocks into well-defined structures, whose properties and functions are regulated in the building block level, still remains very challenging. In this regard, metalloporphyrins would be good building blocks for the construction of such functional materials witnessed by a wide range of molecular architectures, such as molecular boxes, self-assembled arrays, CPs and MOFs with various applications. Particularly, Mn(III)- and Fe(III)-containing metalloporphyrins are often used to fabricate various functional molecular architectures and to mimic the extraordinary behavior of enzymes in both homogeneous and heterogeneous catalytic systems.In the case of homogeneous catalysis, these materials have frequent trouble with fast catalytic degradation because of µ-oxo dimer formation or ligand oxidation. To avoid the catalyst degradation, the heterogenization of homogeneous catalysts, such as immobilization and/or site-isolation of homogeneous catalysts using supporters are widely used alternative strategies. In this regard, I like to present the preparations and heterogeneous catalytic uses of Mn(III)–porphyrin in various porous materials (PMs).