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A: Spectroscopy, Photochemistry, and Excited States
Enhanced Excited-State Proton Transfer via a Mixed Water-Methanol Molecular Bridge of 1-Naphthol-5-Sulfonate in Methanol- Water Mixtures Oren Gajst, Luís Pinto da Silva, Joaquim C.G. Esteves da Silva, and Dan Huppert J. Phys. Chem. A, Just Accepted Manuscript • DOI: 10.1021/acs.jpca.8b00957 • Publication Date (Web): 26 Apr 2018 Downloaded from http://pubs.acs.org on April 27, 2018
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The Journal of Physical Chemistry
Enhanced Excited-State Proton Transfer via a Mixed WaterMethanol Molecular Bridge of 1-Naphthol-5-Sulfonate in MethanolWater Mixtures Oren Gajst,a Luís Pinto da Silva,b,c Joaquim C.G. Esteves da Silvac,d and Dan Hupperta,* a
Raymond and Beverly Sackler Faculty of Exact Sciences, School of Chemistry, Tel Aviv University, Tel Aviv 69978, Israel.
b
Chemistry Research Unit (CIQUP), Department of Chemistry and Biochemistry,
Faculty of Sciences of University of Porto, R. Campo Alegre 687, 4169-007 Porto, Portugal. c
LACOMEPHI, GreenUP, Department of Geosciences, Environment and Territorial
Planning, Faculty of Sciences of University of Porto, R. Campo Alegre 687, 4169-007 Porto, Portugal. d
Chemistry Research Unit (CIQUP), Department of Geosciences, Environment and Territorial Planning, Faculty of Sciences of University of Porto, R. Campo Alegre 687, 4169-007 Porto, Portugal. *Corresponding author: Dan Huppert E-mail:
[email protected] Phone: 972-3-6407012 Fax: 972-3-6407491
Abstract We used steady-state and time-resolved fluorescence techniques to study the excitedstate proton transfer (ESPT) and the non-radiative 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 2.2×1010 s-1, whereas in methanol it is smaller by about three orders of magnitude and is not observed. The ESPT process of 1N5S competes with a major non-radiative process of equal rate and kPT of 2.2×1010 s-1. In methanol-water mixtures of χ H 2O =0.2, the fluorescence lifetime 1 ACS Paragon Plus Environment
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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 - for χ H 2O 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 H 2O
