Designing isomers and elucidating their structure-property relationships are central to advancing chemistry and materials science. Two one-dimensional coordination polymers featuring dual scandium-salen centers are prepared as coordination orientation isomers, sharing identical composition but adopting distinct zigzag or linear chain structures. The zigzag isomer achieves a hydrogen peroxide photosynthesis rate of 0.390 mol gcat.−1 h-1 in an aqueous system employing 1,2,3,4-tetrahydroisoquinoline as sacrificial agent under full-spectrum light, while the linear isomer shows lower activity. A concerted mechanism is revealed, involving co-activation of oxygen and the organic donor through direct proton-coupled electron transfer. The zigzag architecture enhances charge separation via a stronger built-in electric field and stabilizes key co-activation intermediates. In this work, we show that constructing isomeric coordination polymers with tailored spatial and electronic structures provides an avenue for advancing artificial photosynthesis. Zigzag scandium-salen polymer outperforms its linear isomer in H2O2 photosynthesis by enhancing charge separation and stabilizing key intermediates, demonstrating isomer engineering as a route to efficient artificial photosynthesis.
Kong et al. (Thu,) studied this question.