Diketopyrrolopyrrole-Activated Dynamic Condensation Approach to Narrow-Band Gap Vinylene-Linked Covalent Organic Frameworks

Vinyl units intrinsically featuring less steric, nonpolarity, and unsaturated character, are well-known π-bridge used in the synthesis of high-performance semiconducting materials. Two-dimensional (2D) vinylene-linked covalent organic frameworks (COFs) represent a promising class of π-conjugated structures, however, the range of available monomers for the reversible formation of carbon-carbon double bonds remains limited. In this study, a new class of 2D vinylene-linked COFs were synthesized using dimethyldiketopyrrolopyrrole (DM-DPP) as the key monomer. The strong electron deficiency of diketopyrrolopyrrole (DPP) makes its methyl substituents readily activated upon the cocatalysis of L-proline and 4-dimethylaminopyridine in aqueous solution to conduct dynamic condensation with tritopic aromatic aldehydes. The resulting COFs crystallized in an eclipsed AA stacking arrangement and featured abundant, regular nanochannels. Their robust vinyl DPP-linking mode enhanced donor-π-acceptor conjugation and promoted π-stacked alignment along the vertical direction. Consequently, the synthesized COFs exhibited band gaps as narrow as 1.02 eV and demonstrated excellent light-harvesting capability across the visible to near-infrared I (NIR-I) regions. Furthermore, the COFs could be converted into free-standing thin pellets through simple pressure casting, and show excellent photothermal response and cycling stability under different light sources.