Mesoporous Vinylene‐Linked Covalent Organic Frameworks with Heteroatom‐Tuned Crystallinity and Photocatalytic Behaviors

Abstract Owing to its prominent π‐delocalization and stability, vinylene linkage holds great merits in the construction of covalent organic frameworks (COFs) with promising semiconducting properties. However, carbon‐carbon double bond formation reaction always exhibits relatively low reversibility, unfavorable for the formation of high crystalline frameworks through self‐error correction and assembling processes. In this work, we report a heteroatom‐tuned strategy to build up a series of two‐dimensional (2D) vinylene‐linked COFs by Knoevenagel condensation of an electron‐deficient methylthiazolyl‐based monomer with different triformyl substituted (hetero−)aromatic derivatives. The resulting COFs show high‐quality periodic mesoporous structures with high surface areas. Embedding heteroatoms into the backbones enables significantly improving their crystallinity, and finely tailoring their semiconducting structures. Upon visible light stimulation, one of the as‐prepared COFs with donor‐π‐acceptor structure could deliver a nearly seven‐fold increase in the catalytic activity of hydrogen generation as compared with the other two. Meanwhile, in combination with high crystallinity and the matched conduction band energy level, such kind of COFs can be able to selectively generate singlet oxygen and superoxide radicals in a high ratio of up to 30 : 1, allowing for catalyzing aerobic thioanisole oxidation in distinctly tunable activities through the substituent electronic effect of the substrates.