Single-Photon Near-Infrared-Responsiveness from the Molecular to the Supramolecular Level via Platination of Pentacenes.

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.