Vinylene-linked covalent organic frameworks (COFs) are promising photocatalysts owing to their fully conjugated skeletons that facilitate charge carrier mobility. Constructing donor-acceptor (D-A) architectures could further enhance photoinduced charge generation and transport, thus promoting photocatalysis. Therefore, three D-A-type vinylene-linked COFs were fabricated via Knoevenagel polymerization for efficient photocatalysis. By varying the donor moieties from phenyl to 2,5-dimethylbenzene and 3,3’-dimethyl-1,1’-biphenyl in the skeletons, the light-harvesting, optical-bandgap, and charge-transfer properties of the COFs were precisely regulated. All three COFs exhibited attractive photocatalytic hydrogen evolution rates (HERs) upon visible-light irradiation, especially that fabricated using 2,4,6-trimethyl-1,3,5-triazine (TM) and 3,3’-dimethyl[1,1’-biphenyl]-4,4’-dicarboxaldehyde (DMA, TM-DMA-COF). TM-DMA-COF exhibited the strongest D-A interactions, excellent charge-carrier separation and transfer kinetics, and a reduced energy barrier for H₂ formation. Thus, it afforded the highest HER of 4300 µmol h⁻¹ g_cat⁻¹, surpassing those of most state-of-the-art COF photocatalysts. This study provides a simple and effective protocol for modulating the photocatalytic activities of COFs at the molecular level and an interesting insight into the relationship between structural design and photocatalytic performance.

亚乙烯基连接的共价有机骨架 (COF) 是很有前途的光催化剂，因为它们的完全共轭骨架可以促进电荷载流子的迁移。构建供体-受体 (DA) 结构可以进一步增强光诱导电荷的产生和传输，从而促进光催化。因此，通过以下方法制备了三种 DA 型亚乙烯基连接的 COF用于高效光催化的 Knoevenagel 聚合。通过将骨架中的供体部分从苯基变为 2,5-二甲基苯和 3,3'-二甲基-1,1'-联苯，COF 的光捕获、光学带隙和电荷转移特性得到精确控制监管。所有三种 COF 在可见光照射下均表现出极具吸引力的光催化析氢速率 (HER)，尤其是使用 2,4,6-三甲基-1,3,5-三嗪 (TM) 和 3,3'-二甲基制造的 [1, 1'-联苯]-4,4'-二甲醛（DMA、TM-DMA-COF）。TM-DMA-COF 表现出最强的 DA 相互作用、出色的载流子分离和转移动力学，以及降低的 H ₂形成能垒。^{因此，它提供了 4300 µmol h -1} g _cat ^-1的最高 HER，超过了大多数最先进的 COF 光催化剂。本研究为在分子水平上调节 COF 的光催化活性提供了一种简单有效的方案，并为结构设计与光催化性能之间的关系提供了有趣的见解。