Inhibition of light-induced tautomerization of 7-azaindole by phenol: indications of proton-coupled electron/energy transfer quenching

Abstract

The photophysical behavior of a 1:1 complex between phenol and 7-azaindole (7AI) has been investigated in methylcyclohexane solutions at temperatures in the range of 27 to −50 °C. A linear Benesi−Hildebrand plot associated with changes in absorbance of the complex with phenol concentration in the solutions ensures 1:1 stoichiometry of the produced complex. Our estimate for the value of the association constant (K_a) of the complex is ∼120 M^-1 at 27 °C, and it is nearly twice compared to that for 1:1 complex between 7AI and ethanol measured under the same condition. The complexation results in dramatic quenching of the normal fluorescence of 7AI and the process is accelerated upon lowering of temperature. The measured spectra show no indication that phenol promotes tautomerization of 7AI in the excited state. We have argued that the hydrogen bonding between pyridinic N and phenolic O−H (N···O−H) is a vital structural factor responsible for quenching of 7AI fluorescence, and this idea has been corroborated by showing that under same condition the fluorescence of 7AI is enhanced in the presence of anisole. As a plausible mechanism of quenching, we have invoked a proton-coupled electron transfer (PCET) process between phenol and excited 7AI, which outweighs the competing tautomerization process. An analysis in terms of Remm−Weller model reveals that the PCET process involving phenol and excited 7AI could be energetically favorable (ΔG_ET⁰ < 0). An alternative mechanism, where quenching can occur via electronic energy transfer from the excited protonated 7AI to phenoxide ion, following a proton transfer along the N···O−H hydrogen bond, is also discussed.