Photochemistry of “Super”-Photoacids. Solvent Effects
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چکیده
We study steady-state and time-resolved fluorescence of 5-cyano-2-naphthol in various pure solvents. To some of these, excited-state proton transfer occurs within the excited-state lifetime of the chromophore. Solvatochromic shifts in the acid and anion bands are analyzed using the empirical Kamlet-Taft approach. The hydrogen-bond donated from the OH group to basic solvents accounts for most of the shift in the excitation spectra. This bond produces considerably larger shifts in the emission spectra, suggesting that it strengthens in the excited state. In contrast, the hydrogen bond donated from protic solvents to the hydroxyl oxygen is cleaved following photoexcitation. This bond (and not the change in dielectric constant) is responsible for the solvent-induced blue shift in anion fluorescence. Hence it must re-form simultaneously with the protontransfer event. Our time-resolved fluorescence data fit the solution of the Debye-Smoluchowski equation for reversible geminate recombination in a field of force, provided that the difference in excited-state lifetimes and contact quenching are taken into account. An extended theory of reversible geminate recombination provides an accurate description of the asymptotic behavior in this case. The quenching processes correlate with the solvent hydrogen-bond donation ability, implicating the involvement of hydrogen-bonded pathways.
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تاریخ انتشار 1999