Steady-State Spectroscopy to Single Out the Contact Ion Pair in Excited-State Proton Transfer

Despite the outstanding relevance of proton transfer reactions, investigations of the solvent dependence on the elementary step are scarce. We present here a probe system of a pyrene-based photoacid and a phosphine oxide, which forms stable hydrogen-bonded complexes in aprotic solvents of a broad polarity range. By using a photoacid, an excitedstate proton transfer (ESPT) along the hydrogen bond can be triggered by a photon and observed via fluorescence spectroscopy. Two emission bands could be identified and assigned to the complexed photoacid (CPX) and the hydrogen-bonded ion pair (HBIP) by a solvatochromism analysis based on the Lippert-Mataga model. The latter indicates that the difference in the change of the permanent dipole moment of the two species upon excitation is similar to 3 D. This implies a displacement of the acidic hydrogen by similar to 65 pm, which is in quantitative agreement with a change of the hydrogen bond configuration from O-H center dot center dot center dot O to O-center dot center dot center dot H-O+.