Design and synthesis of ultrastable 3D porous aromatic frameworks via stereochemical control of building blocks for hydrogen and methane storage

Achieving ultrahigh porosity together with exceptional framework stability remains a central challenge in the synthetic chemistry of porous materials. Here, we report a stereochemical design strategy to construct three-dimensional backbone frameworks composed exclusively of robust Csp2–Csp2 linkages. Based on this approach, a series of porous aromatic frameworks are synthesized. Among them, PAF-486 exhibits an ultrahigh specific surface area of 5690 m2 g−1. Owing to its Csp2–Csp2 backbone, PAF-486 shows exceptional framework robustness for post-synthetic sulfonation, preserving its framework integrity upon treatment with concentrated sulfuric acid, while the well-known stable porous materials PAF-1 and Cr-based metal–organic frameworks (MOFs) degraded under the same conditions. In addition, its highly open and interconnected pore architecture enables exceptional gas storage performance.