It still remains a challenge to build 3D covalent organic frameworks (COFs) with multiple crossing sets of parallel layers through entanglement due to the complex interactions and spatial constraints among the layers. Herein, the first case of a single-crystal 3D COF with three crossing sets of parallel layers entanglement, namely, USTB-25-3D, was isolated via [3+3] imine condensation reaction between C₃-symmetric building blocks of 1,3,5-trimethyl-2,4,6-tris(4-aminophenyl)benzene and 1,3,5-trimethyl-2,4,6-tris(4-formylphenyl)benzene through hindering π···π stacking by steric hindrance effect. The structure of USTB-25-3D with a resolution up to 1.0 Å was determined using 3D electron diffraction. USTB-25-3D possesses 1.13 nm micropores with a high Brunauer-Emmett-Teller surface area of 3,039 m² g⁻¹, enabling the adsorption of C₂H₂ over CO₂ based on single-component sorption and breakthrough experiments. This work not only presents a unique single-crystal 3D COF with three crossing sets of parallel layers but, more importantly, is helpful toward promoting structural diversity via constructing 3D COFs through inclined entanglement.

由于层间复杂的相互作用和空间限制，通过纠缠构建具有多组交叉平行层的 3D 共价有机框架 (COF) 仍然是一个挑战。在此，通过1的C ₃对称结构单元之间的[3+3]亚胺缩合反应分离出第一个具有三组交叉平行层纠缠的单晶3D COF，即USTB-25-3D，3,5-三甲基-2,4,6-三(4-氨基苯基)苯和1,3,5-三甲基-2,4,6-三(4-甲酰基苯基)苯通过阻碍π·π堆积位阻效应。使用 3D 电子衍射确定了 USTB-25-3D 的结构，分辨率高达 1.0 Å。 USTB-25-3D拥有1.13 nm的微孔和3,039 m ² g ^-1的高Brunauer-Emmett-Teller表面积，基于单组分吸附和突破性实验，能够在CO ₂上吸附C ₂ H ₂ 。这项工作不仅提出了一种具有三组交叉平行层的独特单晶3D COF，更重要的是，通过倾斜纠缠构建3D COF有助于促进结构多样性。