Fluoroalkyl phthalocyanines: Bioinspired catalytic materials

Abstract

The design of self oxidation-resistant catalytic materials based on organic molecules, although advantageous due to the ability to control their structures, is limited by the presence of labile C–H bonds. This mini review summarizes recent work aimed at first-row transition metal complexes of a new class of coordinating ligands, fluoroalkyl-substituted fluorophthalocyanines, R[Formula: see text]Pcs, ligands in which all, or the majority of their C–H bonds are replaced by a combination of fluoro- and perfluoroalkyl groups yielding porphyrin-bioinspired catalyst models. In the case of homogeneous systems, cobalt(II) complexes catalyze the aerobic oxidation of thiols to disulfides, a reaction of both biological significance and industrial importance. Zinc(II) complexes photo-generate excited state singlet oxygen, [Formula: see text]O[Formula: see text], resulting in both the incorporation of O[Formula: see text] in C–H bonds or, depending on the reaction parameters, oxidation of dyes, model pollutants. Catalyst heterogenization using oxidic and other supports yields stable, active hybrid materials. Functionalized R[Formula: see text]Pcs with acidic (–COOH) or basic (–NH[Formula: see text]R[Formula: see text], [Formula: see text] 2) groups exhibit scaffolds that afford both conjugation with biological vectors for theranostic applications as well as solid-supported materials with superior stability. Electrodes modified with hybrid R[Formula: see text]Pc-containing supports have also been used in photo-oxidations, replacing enzymes and H[Formula: see text]O[Formula: see text] associated reagents with a combination of light and air. An analytical device employed for the nano-level detection of environmentally deleterious antibiotics has been constructed.