Construction of Thiadiazole‐Linked Covalent Organic Frameworks via Facile Linkage Conversion with Superior Photocatalytic Properties

The establishment of facile synthetic routes to engineer covalent organic frameworks (COFs) with fully conjugated structure and excellent stability is highly desired for practical applications in optoelectronics and photocatalysis. Herein, a novel linkage conversion strategy is reported to prepare crystalline thiadiazole‐linked COFs via thionation, cyclization, and oxidation of N‐acylhydrazole bonds with Lawesson's reagent (LR). The as‐prepared thiadiazole‐linked COFs not only remain porosity and crystallinity, but enhance its chemical stability. Furthermore, thiadiazole‐linked COFs are more favorable to lower exciton binding energy and promote π‐electron delocalization over the whole reticular framework than N‐acylhydrazone‐linked COFs. Notably, the extended π‐conjugation structure and decent crystallinity of the resulting TDA‐COF are reflected by its higher photocatalytic H(2) evolution rate (61.3 mmol g(−1) in 5 h) in comparison with that (7.5 mmol g(−1)) of NAH‐COF.