The exploration of highly crystalline three-dimensional (3D) covalent organic frameworks (COFs) with new topologies remains challenging. In this work, we rationally designed and synthesized two highly crystalline 3D COFs, constructed by an octatopic linker and porphyrin-based tetratopic linkers through an [8 + 4] approach. The COF structures were successfully determined as non-interpenetrated scu topology using the continuous rotation electron diffraction (cRED) technique and structural simulation. The scu network was further verified by both high-resolution transmission electron microscopy (TEM) and pore size distribution based on N₂ sorption isotherms. Due to the exposed catalytic porphyrin sites, good photoelectric activity, and high structure robustness, these COFs can serve as highly efficient heterogeneous photocatalysts for various reactions, including oxidative amine coupling and cycloaddition reactions between tertiary aniline and maleimide, with a broad substrate scope (22 examples). This work enriches the topological varieties of 3D COFs and provides a class of highly efficient photocatalysts.

探索具有新拓扑结构的高结晶三维 (3D) 共价有机框架 (COF) 仍然具有挑战性。在这项工作中，我们合理设计并合成了两个高度结晶的 3D COF，它们由八位连接子和基于卟啉的四位连接子通过 [8 + 4] 方法构建。使用连续旋转电子衍射 (cRED) 技术和结构模拟成功地将 COF 结构确定为非互穿scu拓扑结构。通过高分辨率透射电子显微镜 (TEM) 和基于 N _{2的孔径分布进一步验证了}scu网络吸附等温线。由于暴露的催化卟啉位点、良好的光电活性和高结构稳健性，这些 COF 可以作为高效的多相光催化剂用于各种反应，包括叔苯胺和马来酰亚胺之间的氧化胺偶联和环加成反应，具有广泛的底物范围（22例子）。这项工作丰富了3D COFs的拓扑种类，提供了一类高效光催化剂。