Tetrazine-Linked Covalent Organic Frameworks With Acid Sensing and Photocatalytic Activity

The first synthesis and comprehensive characterization of two vinyl tetrazine-linked covalent organic frameworks (COF), TA-COF-1 and TA-COF-2, are reported. These materials exhibit high crystallinity and high specific surface areas of 1323 and 1114 m² g⁻¹. The COFs demonstrate favorable band positions and narrow band gaps suitable for light-driven applications. These advantages enable TA-COFs to act as reusable metal-free photocatalysts in the arylboronic acids oxidation and light-induced coupling of benzylamines. In addition, these TA-COFs show acid sensing capabilities, exhibiting visible and reversible color changes upon exposure to HCl solution, HCl vapor, and NH₃ vapor. Further, the TA-COFs outperform a wide range of previously reported COF photocathodes. The tetrazine linker in the COF skeleton represents a significant advancement in the field of COF synthesis, enhancing the separation efficiency of charge carriers during the photoreaction and contributing to their photocathodic properties. TA-COFs can also degrade 5-nitro-1,2,4-triazol-3-one (NTO), an insensitive explosive present in industrial wastewater, in 20 min in a sunlight-driven photocatalytic process; thus, revealing dual functionality of the protonated TA-COFs as both photodegradation and Brønsted acid catalysts. This pioneering work opens new avenues for harnessing the potential of the tetrazine linker in COF-based materials, facilitating advances in catalysis, sensing, and other related fields.