Isomerization‐Accelerated Exciton Kinetics in PDI Linear Conjugated Polymers for High‐Efficiency Photocatalytic Oxygen Evolution

Understanding and substantively accelerating exciton kinetics in perylene diimide (PDI)-based linear conjugated polymers (LCPs) represents a promising yet challenging frontier in the field of photocatalysis. Herein, an isomerization strategy is proposed to construct two PDI-based LCPs through bridge-bond isomerization to induce π-stacking to finely modulate charge distribution, and the obtained maleamide-PDI exhibits excellent activity for sacrificial-agent-assisted photocatalytic oxygen evolution with a remarkable apparent quantum yield of 13.4% at 380 nm, surpassing the majority of reported organic polymer photocatalysts. Theoretical calculations combined with in situ Fourier transform infrared spectra reveal that isomerization-induced high crystallinity with tight π-stacking and efficient spatial exciton separation activate the carbonyl group located at the bridging chain, endowing it with high photocatalytic activity. This work pioneers the use of isomerization for modifying PDI-based LCPs, highlighting the pivotal role of exciton acceleration in photocatalysis and providing guidance for the isomerized design of PDI-LCPs.