Heterogenization of porphyrin as single molecular heterogeneous catalyst for highly recyclable and selective photocatalytic oxidation of sulfides

Abstract

Precise design and synthesis of supramolecules with cavities are of vital importance for developing novel porous heterogeneous catalysts but remain great challenges. Herein, taking advantage of configuration-controllable capability, four bulky and rigid EMind scaffolds were peripherally installed onto photocatalytic porphyrin core to construct metalloporphyrin with semi-opened cavity as single molecular heterogeneous catalyst. The extremely low solubility in organic solvents and incapability of close packing endowed this kind of material with intriguing intramolecular porosity and heterogenization in catalysis. Among them, the porphyrin(Fe) molecule engaging the advantages of both homogeneous and heterogeneous catalysts possessed good stability, recyclability and high efficiency to oxidize various sulfides into sulfoxides in gram-scale, attributable to the designed novel structure. The key reactive oxygen species was demonstrated to be superoxide anion radicals in the established catalytic system.