Modulating π-bridge in donor-π-acceptor covalent organic frameworks for low-energy-light-driven photocatalytic reaction.

Most of the photocatalytic reactions are currently driven by high-energy light (UV, blue light), which inevitably leads to side reactions and co-catalyst deactivation. Therefore, there is an urgent need to prepare novel photocatalysts with low-energy photocatalytic properties. Herein, we report a rational molecular design of covalent organic frameworks (COFs) equipped with donor-π-acceptor systems with different π-bridges (aromatic ring, mono- and bis-alkynyl). It was found that the COF with mono-alkynes as a π-bridge (TP-EDAE) can accelerate the rapid carrier migration even under low-energy light compared to the other two types of π-bridges (aromatic ring and bis-alkynyl), which was conducive to the photocatalytic redox reactions. As a result, the TP-EDAE samples showed high CO coupling activity and good substrate versatility under both high-energy light (blue light) and low-energy light (green light), especially the TP-EDAE samples displayed high stability with no obvious activity decay within five cycles under low-energy light. This work highlights the fundamental molecular design of advanced functionalized COFs with specific π-bridges for photocatalytic organic reactions under low-energy light.