Excited‐State Proton Transfer Dynamics of a Super‐Photoacid in Acetone‐Water Mixtures

Super‐photoacids, that is, photoacids with a negative pKa value in the electronically excited state, can trigger an excited‐state proton transfer (ESPT) to the solvent. For the neutral pyranine‐derived super‐photoacid studied here, even indications for ESPT in acetoneous solution are reported. The characteristics of ESPT in this environment, that is, which intermediates exist and what the impact of cosolvents is, remain unsettled though. In this work, we study ESPT in acetone‐water mixtures by steady‐state and time‐resolved fluorescence spectroscopy. Various effects are observed: First, the addition of water supports the formation of a hydrogen‐bonded ground‐state complex comprising one water molecule and the photoacid, whose excitation triggers the formation of a hydrogen‐bonded ion pair on a sub‐ns time scale. Second, water has an overall accelerating effect on the fluorescence dynamics of the involved emitting species, whose contributions are disentangled in a global analysis scheme, enabling the identification of emission from the free photoacid, a photoacid‐water complex, a hydrogen‐bonded ion pair, and the deprotonated photoacid. At least two water molecules are necessary for ESPT in the environment. Third, additional acidification thwarts an efficient ground‐state complex formation of the photoacid and water. However, upon excitation, complexation may occur on a timescale faster than the photoacid's excited‐state lifetime, so that emission from a nascent complex emerges. Let's get rid of the proton: Under acetoneous conditions with water as a cosolvent, the excited‐state proton transfer (ESPT) of a pyrene‐based super‐photoacid exhibits emission dynamics originating from the free photoacid ROH*, a photoacid‐water complex CPX*, a hydrogen‐bonded ion pair HBIP*, and the deprotonated photoacid RO−*. One water molecule is not sufficient for accepting the proton. Additional acidification counteracts both the ground‐state formation of CPX and the passage of the ESPT cascade towards RO−*.