Dielectric stabilization controls excited-state proton transfer and ion pair dynamics in organic solvents

Excited-state proton transfer (ESPT) in aprotic organic solvents has received limited attention due to their inability to accept protons. However, bimolecular ESPT from a photoacid to an organic base in such media enables systematic studies on the influence of macroscopic solvent parameters on the ESPT as demonstrated in this work. The full photocycle starting from initial deprotonation in a hydrogen-bonded donor-acceptor complex to full dissociation in the excited state followed by slow recombination in the ground state was characterized by various spectroscopic methods in solvent mixtures of varying polarity. The initial deprotonation producing contact ion pairs is ultrafast (sub-100 fs) and requires minimal solvent reorganization. The contact ion pairs dissociate <i>via</i> a distinct intermediate, the so-called solvent-separated ion pair, preceding the fully dissociated free ion pairs. The time scale of the ion pair dynamics is dominated by viscosity whereas the yield is determined by the polarity. In low polarity solvents (<i>ε</i> _r < 10), the population is trapped as solvent-separated ion pairs and full dissociation becomes operative only at intermediate polarity. Ground-state recombination of the intermediate ion pair species is fast and thus a significant population of fully dissociated ground-state ions is produced only above intermediate polarities.