Toward Pore Size-Selective Photoredox Catalysis Using Bifunctional Microporous 2D Triazine-Based Covalent Organic Frameworks.

The design and synthesis of photoactive metal-free 2D materials for selective heterogeneous photoredox catalysis continue to be challenging due to issues related to nonrecyclability, and limited photo- and chemical stability. Herein, we report the photocatalytic properties of a triazine-based porous COF, TRIPTA, which is found to be capable of facilitating both SET (single electron transfer) for photocatalytic reductive debromination of phenacyl bromide in absence of oxygen and generation of reactive oxygen species (ROS) for benzylamine photo-oxidation in the presence of oxygen, respectively, under visible light irradiation. Inspired by the latter results, we further systematically investigated different-sized benzylamine substrates in this single-component reaction and compared the results with an analogous COF (Micro-COF-2) exhibiting a larger pore size. We observed a marked improvement in the conversion of larger-sized substrates with the latter COF, thereby demonstrating angstrom-level pore size-selective photocatalytic activity of COFs.