A Strongly Reducing sp 2 Carbon‐Conjugated Covalent Organic Framework Formed by N ‐Heterocyclic Carbene Dimerization

• Published in: Angewandte Chemie 2024-10
• Main Authors: Pitt, Tristan A., Azbell, Tyler J., Kim, Jaehwan, Shi, Zixiao, Muller, David A., Addicoat, Matthew A., Milner, Phillip J.
• Format: Article
• Language: English
• ISSN: 0044-8249; 1521-3757
• DOI: 10.1002/ange.202416480

Covalent organic frameworks linked by carbon‐carbon double bonds (C=C COFs) are an emerging class of crystalline, porous, and conjugated polymeric materials with potential applications in organic electronics, photocatalysis, and energy storage. Despite the rapidly growing interest in sp 2 carbon‐conjugated COFs, only a small number of closely related condensation reactions have been successfully employed for their synthesis to date. Herein, we report the first example of a C=C COF, CORN‐COF‐1 (CORN=Cornell University), prepared by N ‐heterocyclic carbene (NHC) dimerization. In‐depth characterization reveals that CORN‐COF‐1 possesses a two‐dimensional layered structure and hexagonal guest‐accessible pores decorated with a high density of strongly reducing tetraazafulvalene linkages. Exposure of CORN‐COF‐1 to tetracyanoethylene (TCNE, E 1/2 =0.13 V and −0.87 V vs. SCE) oxidizes the COF and encapsulates the radical anion TCNE⋅ − and the dianion TCNE 2− as guest molecules, as confirmed by spectroscopic and magnetic analysis. Notably, the reactive TCNE⋅ − radical anion, which generally dimerizes in the solid state, is uniquely stabilized within the pores of CORN‐COF‐1. Overall, our findings broaden the toolbox of reactions available for the synthesis of redox‐active C=C COFs, paving the way for the design of novel materials.