Journal or Book Title
Structure and Reactivity in Aqueous Solution
ACS Symposium Series
The nonradiative pathways of 7-azaindole are extremely sensitive to solvent. In alcohols, 7-azaindole executes an excited-state double-proton transfer. In water, this tautomerization is frustrated. Proton inventory experiments suggest a concerted double-proton transfer in the alcohols and point to another nonradiative process in water. We propose the following idealized picture. Whereas at room temperature 7-azaindole can form a cyclic hydrogen-bonded intermediate with a single alcohol molecule facilitating tautomerization, in water more than one solvent molecule coordinates to the solute and thus prohibits the concerted process. More detailed measurements, however, indicate that water and alcohols do not solvate 7-azaindole in fundamentally different ways, but rather that they represent two extremes of the same phenomenon.
American Chemical Society
Gai, F.; Rich, R. L.; Chen, Y.; and Petrich, Jacob W., "Probing Solvation by Alcohols and Water with 7-Azaindole" (2009). Chemistry Publications. 815.