Solvent Effect on Excited State Proton Transfer Mechanism of 8-Amino-2-Naphthol

Photoacids, compounds that undergo excited state proton transfer (ESPT), have been utilized in different solar energy and lithographic applications.1, 2 The addition of functional groups and solvent can both change the ESPT mechanism of photoacids. In this study, the effect of solvent on the ESPT mechanism was explored using a model diprotic photoacid, 8-amino-2-naphthol (8N2OH). The photochemistry of 8N2OH in water and common nonaqueous solvents, acetonitrile, tetrahydrofuran (THF), and methanol, were studied using UV/Vis absorption, steady-state emission, and time-correlated single photon counting (TCPSC) emission spectroscopy. The results were analyzed using the Kamlet-Taft parameters. It was found that the ESPT mechanism of the cation in water is different from the mechanism in acetonitrile and THF. In water the excited cation forms the zwitterion, i.e. the OH site undergoes ESPT, while in acetonitrile and THF, the excited cation forms the neutral species, i.e. the NH3+ site undergoes ESPT. No ESPT was observed for 8N2OH in methanol. The effect of solvent mixtures on photoacidity was also investigated using acetonitrile and water mixtures. The solvent effects were more subtle; the time-resolved emission measurements showed the greatest stabilization of the excited neutral 8N2OH species at 20/80% acetonitrile-water mixtures. Finally, the ability to extend the solvent studies to ionic liquids, 1-ethyl-3-methylimidazolium (Im) trifluromethanesulfonate (OTF), was demonstrated. The combined studies reveal that solvent plays a large role in determining the ESPT mechanism and stabilization of 8N2OH.