Programming Tetrathiafulvalene‐Based Covalent Organic Frameworks for Promoted Photoinduced Molecular Oxygen Activation

Abstract Despite the pivotal role of molecular oxygen (O 2 ) activation in artificial photosynthesis, the activation efficiency is often restricted by sluggish exciton dissociation and charge transfer kinetics within polymer photocatalysts. Herein, we propose two tetrathiafulvalene (TTF)‐based imine‐linked covalent organic frameworks (COFs) with tailored donor‐acceptor (D–A) structures, TTF‐PDI‐COF and TTF‐TFPP‐COF, to promote O 2 activation. Because of enhanced electron push‐pull interactions that facilitated charge separation and transfer behavior, TTF‐PDI‐COF exhibited superior photocatalytic activity in electron‐induced O 2 activation reactions over TTF‐TFPP‐COF under visible light irradiation, including the photosynthesis of ( E )‐3‐amino‐2‐thiocyano‐ α , β ‐unsaturated compounds and H 2 O 2 . These findings highlight the significant potential of the rational design of COFs with D–A configurations as suitable candidates for advanced photocatalytic applications.