Quantifying the Ground‐State Hydrogen‐Bond Formation of a Super‐Photoacid by Inspecting Its Excited‐State Dynamics

The identification and quantification of hydrogen (H)‐bonded complexes form the cornerstone of reaction‐mechanism analysis in ultrafast proton transfers. Traditionally, the Benesi‐Hildebrand method has been employed to obtain the formation constants of H‐bonded complexes, given that H‐bonding additives induce an alteration in spectral features exclusively through H‐bond formation. However, if the additive introduction impacts the bulk polarity of the solution, inducing a spectral shift, the spectroscopic method's accuracy in analyzing the H‐bond formation becomes compromised. In this study, we scrutinize H‐bond formation under the influence of an H‐bond accepting solute in an aprotic solvent. This is achieved by quantifying the fractions of two concurrent pathways involved in the excited‐state proton transfer (ESPT) of a super‐photoacid: the ultrafast ESPT of an H‐bonded complex vs. the diffusion‐controlled ESPT of the free acid. Our method offers improved accuracy compared to conventional steady‐state spectroscopic techniques, by directly quantifying the H‐bonded complexes using the time‐resolved spectroscopic method, thereby circumventing the aforementioned limitation.