Heteroatom-Embedded Approach to Vinylene-Linked Covalent Organic Frameworks with Isoelectronic Structures for Photoredox Catalysis

Embedding heteroatoms into the main backbones of polymeric materials has become an efficient tool for tailoring their structures and improving their properties. However, owing to comparatively harsh heteroatom-doping conditions, this has rarely been explored in covalent organic frameworks (COFs). Herein, upon aldol condensation of a trimethyl-substituted pyrylium salt with a tritopic aromatic aldehyde, a two-dimensional oxonium-embedded COF with vinylene linkages was achieved, which was further converted to a neutral pyridine-cored COF by in situ replacement of oxonium ions with nitrogen atoms under ammonia treatment. The two heteroatom-embedded COFs are conceptually isoelectronic with each other, featuring similar geometric structures but different electronic structures, rendering them capable of catalyzing the visible-light-promoted multi-component synthesis of tri-substituted pyridine derivatives with good recyclability.

Automated summary

The researchers have successfully achieved a two-dimensional oxonium-embedded COF with vinylene linkages and converted it to a neutral pyridine-cored COF through ammonia treatment. These two heteroatom-embedded COFs, while featuring similar geometric structures, exhibit different electronic structures, and are capable of catalyzing multi-component synthesis with good recyclability.