Near-infrared (NIR) responsiveness is important for various applications.Currently,single-photon NIR-responsive systems are rare compared to systems that display two-photon absorption and triplet-triplet annihilation processes.S upramolecular stacking of photo-responsive chromophores results in decreased efficiency due to space-confinement effects. Herein we showt hat s-platination of pentacenes is af easible protocol to build single-photon NIR-responsive systems,w ith advantages including alow HOMO-LUMO energy gap,high photochemical efficiency,a nd pathways pecificity.T he pentacene-to-endoperoxidation transformation is accompanied by color and absorbance changes.T he high photo-oxygenation efficiency of s-platinated pentacenes facilitates NIR responsiveness in one-dimensional supramolecular polymers,r esulting in the disappearance of supramolecular chirality signals and disruption of self-assembled nanofibers.O verall, the splatination strategy opens up new avenues toward NIR photoresponsive materials at the molecular and supramolecular levels.

Chiral supramolecular polymerization of π-conjugated molecules has become a feasible route toward circularly polarized luminescence (CPL) materials. It remains challenging to solve emission quenching and/or chiral contamination issues upon supramolecular...

Near‐infrared (NIR) responsiveness is important for various applications. Currently, single‐photon NIR‐responsive systems are rare compared to systems that display two‐photon absorption and triplet–triplet annihilation processes. Supramolecular stacking of photo‐responsive chromophores results in decreased efficiency due to space‐confinement effects. Herein we show that σ‐platination of pentacenes is a feasible protocol to build single‐photon NIR‐responsive systems, with advantages including a low HOMO–LUMO energy gap, high photochemical efficiency, and pathway specificity. The pentacene‐to‐endoperoxidation transformation is accompanied by color and absorbance changes. The high photo‐oxygenation efficiency of σ‐platinated pentacenes facilitates NIR responsiveness in one‐dimensional supramolecular polymers, resulting in the disappearance of supramolecular chirality signals and disruption of self‐assembled nanofibers. Overall, the σ‐platination strategy opens up new avenues toward NIR photo‐responsive materials at the molecular and supramolecular levels.