Three-dimensional (3D) covalent organic frameworks (COFs) possess higher surface areas, more abundant pore channels, and lower density compared to their two-dimensional counterparts which makes the development of 3D COFs interesting from a fundamental and practical point of view. However, the construction of highly crystalline 3D COF remains challenging. At the same time, the choice of topologies in 3D COFs is limited by the crystallization problem, the lack of availability of suitable building blocks with appropriate reactivity and symmetries, and the difficulties in crystalline structure determination. Herein, we report two highly crystalline 3D COFs with pto and mhq-z topologies designed by rationally selecting rectangular-planar and trigonal-planar building blocks with appropriate conformational strains. The pto 3D COFs show a large pore size of 46 Å with an extremely low calculated density. The mhq-z net topology is solely constructed from totally face-enclosed organic polyhedra displaying a precise uniform micropore size of 1.0 nm. The 3D COFs show a high CO₂ adsorption capacity at room temperature and can potentially serve as promising carbon capture adsorbents. This work expands the choice of accessible 3D COF topologies, enriching the structural versatility of COFs.

与二维共价有机框架 (COF) 相比，三维 (3D) 共价有机框架 (COF) 具有更高的表面积、更丰富的孔道和更低的密度，这使得 3D COF 的开发从基础和实用的角度来看很有趣。然而，高度结晶的 3D COF 的构建仍然具有挑战性。同时，3D COF 中拓扑的选择受到结晶问题、缺乏具有适当反应性和对称性的合适构建块的可用性以及晶体结构确定困难的限制。在此，我们报告了两种具有 pto 和 mhq-z 拓扑结构的高度结晶 3D COF，通过合理选择具有适当构象应变的矩形平面和三角形平面构建块来设计。pto 3D COF 显示出 46 Å 的大孔径和极低的计算密度。mhq-z 网络拓扑完全由完全封闭的有机多面体构成，显示出 1.0 nm 的精确均匀微孔尺寸。3D COF 显示高 CO₂室温下的吸附能力，可作为有前途的碳捕获吸附剂。这项工作扩展了可访问的 3D COF 拓扑结构的选择，丰富了 COF 的结构多功能性。