Triazine–Porphyrin-Based Hyperconjugated Covalent Organic Framework for High-Performance Photocatalysis

Covalent organic frameworks (COFs) with porphyrins as structural units are a new kind of porous organic polymers, which have a regular and ordered structure, abundant porosity, and good stability. In the past, the construction of porphyrin COFs was generally synthesized by routes such as a Schiff base reaction. Here, we report a new COF structure by linking the porphyrin with the triazine ring. Using a cyano group-terminated porphyrin as a structural unit precursor, a new triazine-porphyrin hyperconjugated COF (TA-Por-sp²-COF) was constructed through the cyano group's self-polymerization. The extension of porphyrin units in two directions that stemmed from the cyano group at para-positions accounts for the establishment of a highly ordered two-dimensional topological structure. Attributing to the collaboration of electron-donating and withdrawing blocks for photo-induced carrier separation and adequate porosity for mass diffusion, this hyperconjugated system showed high photocatalytic performance in organic reactions such as the aerobic coupling reaction of benzylamine and thioanisole selective oxidation.