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

Despite the pivotal role of molecular oxygen (O2) 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 O2 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 O2 activation reactions over TTF‐TFPP‐COF under visible light irradiation, including the photosynthesis of (E)‐3‐amino‐2‐thiocyano‐α,β‐unsaturated compounds and H2O2. These findings highlight the significant potential of the rational design of COFs with D‐A configurations as suitable candidates for advanced photocatalytic applications.