Anchoring Zn-phthalocyanines in the pore matrices of UiO-67 to improve highly the photocatalytic oxidation efficiency

Abstract Metallophthalocyanines (MPcs) with unique photoelectronic properties are a class of very promising photosensitizers for highly efficient photocatalysis; however, their photocatalytic applications are heavily frustrated by the strong π-π self-aggregation issue. We report herein a partial ligand substitution strategy to imbed MPcs in the pore matrices of metal-organic frameworks (MOFs), which could significantly improve the photocatalytic efficiency of MPcs by prohibiting their cofacial self-aggregation. We successfully incorporate ZnPc moieties into the pore matrices of MOF UiO-67 by partially replacing the pristine 4,4′-biphenyldicarboxylate (BPDC) ligands with four-branched ZnPc ligands, in which the ZnPc photosensitizers are easily accessed to reactant molecules in photocatalysis by taking the advantages of porous MOF UiO-67. The ZnPc-incorporated MOF UiO-67-ZnPc demonstrates high photocatalytic efficiency and selectivity in aerobic oxidation of naphthols to produce highly value-added naphthoquinones with high photoactivity, stability and broad substrate applicability under visible light irradiation, which is much superior to its molecular counterpart.