Crystalline and Stable Benzofuran-Linked Covalent Organic Frameworks from Irreversible Cascade Reactions

We report the synthesis of crystalline two-dimensional covalent organic frameworks (COFs) by connecting hydroxybenzene-aldehyde and acetonitrile building blocks to form cyano-substituted benzofuran linkages. Unlike the majority of COFs that were synthesized based on condensation reactions, the COFs in this report are crystallized from irreversible cascade reactions involving consecutive cyanide migration, ring-closure, and oxidation reactions. The irreversible property endows the COFs with high chemical stability in both acid and base and allows them to be postsynthetically modified to install predesigned functionality under harsh conditions. We highlight that the functionalized COFs serve as exceptional vehicles for superprotonic conductions.