화학공학소재연구정보센터
Journal of Physical Chemistry A, Vol.123, No.1, 48-58, 2019
Enhanced Excited-State Proton Transfer via a Mixed Methanol-Water Molecular Bridge of 1-Naphthol-3,6-disulfonate in Methanol-Water Mixtures
Steady-state and time-resolved fluorescence techniques were used to study the excited-state proton transfer (ESPT) from an irreversible photoacid, 1-naphthol-3,6-disulfonate (1NP36DS), to methanol water mixtures. We found that at X-water = 0.3 the ESPT rate constant is higher by a factor of 10 that in neat methanol. TD-DFT calculations show that a mixed molecular bridge of two methanol molecules and one water molecule enables the ESPT from the 1-OH to the 3-sulfonate. The RO-(S-1) state is stable by -2.5 kcal/mol in comparison to the ROH(S-1) state. We compare the ESPT rate constants of a reversible photoacid, 8-hydroxy-1,3,6-pyrene-trisulfonate (HPTS), in the same methanol water mixtures. At X-water approximate to 0.3 the ESPT rate constant of HPTS increased by only 15%. We explain the large difference of the ESPT rate of 1NP36DS by the formation of a water bridge or a mixed methanol-water bridge from 1-OH to one of the sulfonates and the absence of such a bridge in HPTS. The water or mixed methanol-water bridge of 1NP36DS enhances the ESPT rate in methanol-water mixtures of low water mole ratio.