Rational Construction of Borromean Linked Crystalline Organic Polymers

Abstract Attributed to the unique topological complexity and elegant beauty, Borromean systems are attracting intense attention. However, at present, the construction of Borromean linked organic polymers remains a challenge. To address this formidable challenge, we developed a supramolecular‐synthon‐driven approach to fabricate Borromean linked organic polymer. The solvothermal condensation reaction of a judiciously selected trigonal pyramidal building block, 1,3,5‐Tris(4‐aminophenyl)adamantane, with linear dialdehyde building blocks allowed the construction of two rare covalent organic frameworks (COFs) with high crystallinity and robustness. Structure refinement unveiled the successful formation of entangled 2D→2D Borromean arrayed structures. Both the two COFs were of microporosity and thus demonstrated the potentials for gas separation. The successful synthesis of the first two Borromean linked organic polymers paves the avenue to expand the supramolecular‐synthon‐driven approach to other building blocks and topologies, and broadens the family and scope of COFs.