Enhanced Excited-State Proton Transfer via a Mixed Water-Methanol Molecular Bridge of 1-Naphthol-5-Sulfonate in Methanol-Water Mixtures.

We used steady-state and time-resolved fluorescence techniques to study the excited-state proton transfer (ESPT) and the nonradiative properties of two irreversible photoacids, 1-naphthol-4-sulfonate (1N4S) and 1-naphthol-5-sulfonate (1N5S). We found that the ESPT rate constant of 1N4S in water is 2.2 × 10 s, whereas in methanol, it is smaller by about 3 orders of magnitude and is not observed. The ESPT process of 1N5S competes with a major nonradiative process of equal rate and k of 2.2 × 10 s. In methanol-water mixtures of χ = 0.2, the fluorescence lifetime of the ROH form of 1N5S is lower by a factor of 10 than that in pure methanol. In the steady-state fluorescence spectra of 1N5S in methanol-water mixtures, there are two iso-emissive points, one for χ < 0.2 and one for χ > 0.3. This large reduction in fluorescence intensity and the two iso-emissive points are explained by the existence of a mixed water-methanol bridge of about three molecules that connects the proton donor 1-OH with the 5-sulfonate in mixtures of χ < 0.2. The bridge enhances both the ESPT and the nonradiative processes. For 1N4S in methanol-water mixtures at χ ≈0.2, the reduction in the fluorescence lifetime is only by ∼30%, and only one iso-emissive point exists in the steady-state fluorescence spectra for 0 <χ < 1. TD-DFT computations show that a mixed bridge of one water molecule and two methanol molecules that connects the 1-OH with 5-sulfonate is more stable by 7.7 kcal/mol than the 1-OH reactant in the S state, and the barrier is only 8.0 kcal/mol. The nonradiative channel is because the S dark state is about 4.6 kcal/mol higher than the S state.