Single-Photon Near Infrared Responsiveness From Molecular to Supramolecular Levels via Platination of Pentacenes.

Near-infrared (NIR) responsiveness is important for various applications. Currently, single-photon NIR-responsive systems are rare compared to those achieved by two-photon absorption and triplet-triplet annihilation processes. Supramolecular stacking of photo-responsive chromophores results in the decreased efficiency due to the space confining effects. To address these issues, herein σ -platination of pentacenes is served as a feasible protocol to build single-photon NIR-responsive systems, which brings advantages including low HOMO-LUMO energy gap, high photo-chemical 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, giving rise to 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 molecular and supramolecular levels.