Abstract
Molecular architectures offering large cavities can accommodate guest molecules, while their compositional engineering allows tunability of the band gap to support photocatalysis using visible light. In this work, two lanthanide (Ln)-based macrocycles, synthesized using a cobalt-based metalloligand and offering large rectangular cavities, exhibited selective adsorption of neutral dyes over both anionic and cationic dyes. Both Ln macrocycles illustrated complete photodegradation of cationic dyes using visible light without the use of any oxidant. Both Ln macrocycles exhibited complete photodegradation of not only cationic dyes but also a few phenothiazine-based antipsychotic drugs. Photocatalysis involved the generation of reactive oxygen species (ROS), which was corroborated with the band gap of two Ln macrocycles. These results were supported by radical scavenger studies and the quantitative estimation of superoxide and hydroxyl radicals. Complete photodegradation of both dyes and drugs was confirmed by spectral studies, while the generation of CO2 and N2 gases was established by gas chromatography. Importantly, Ln macrocycles were able to distinguish between the neutral dyes that were quantitatively adsorbed and the cationic dyes/drugs that were completely photodegraded.
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