Aim of the experiment

The photophysical behavior of a 1:1 complex between phenol and 7-azaindole (7AI) has been
investigated in methylcyclohexane solutions. 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. The measured spectra show no indication that phenol
promotes tautomerization of 7AI in the excited state. The hydrogen bonding between pyridinic N
and phenolic O-H (N…O-H) is a vital structural factor responsible for quenching of 7AI fluorescence.

Introduction
The complex is easily produced upon mixing phenol and 7AI in a hydrocarbon solution. Figure 1
shows the changes S1 to S0 absorption of 7AI in a dilute methylcyclohexane owing to a successive
increase of phenol concentration in the solution.

Figure 1. Changes in the S1 to S0 absorption spectrum of 7AI upon complexation with phenol
(PhOH) in methylcyclohexane at room temperature. The traces 1-4 denote the spectra
recorded for 7AI solution (10-5 M) with different concentration of phenol as mentioned in the
figure.
The 1:1 nature of the complex is ascertained by observing a linear Benesi-Hildebrand plot associated
with changes in the absorption of the complex at 304 nm with increasing concentration of phenol.

Figure 2. Benesi-Hildebrand plot showing changes in absorbance at 304 nm of the 7AI-

phenol complex with an increase in concentration of the phenol in the methylcyclohexane
solution of 7AI (10-5 M).
To investigate the catalytic effect of phenol on the excited-state tautomerization of 7AI in 1:1 doubly
hydrogen-bonded complex configuration, a set of fluorescence spectra has been measured with
mixed solutions containing 7AI (10-5 M) and phenol of different concentrations in the range of
3.33*10-3 to 3.33*10-2 M. Three such spectra are presented in Figure 3 (traces 2-4) along with that of
the pure solution of 7AI (trace 1). All the spectra are measured at room temperature by exciting at
300 nm.

Figure 3. Fluorescence spectra of 7AI in methylcyclohexane (10-5 M) at room temperature in

the presence of three different concentrations of phenol (traces 1-4). The fluorescence
excitation spectra for the same set of mixed and pure 7AI solutions are presented in the inset
(traces 1-4). The excitation spectra are recorded by probing the emission at 380 nm.
It is worth mentioning that the sharp bands displayed on each of the spectra at 312 and 324 nm are
the Raman bands of the solvent, because they show up in the same way in the emission spectrum of
pure methylcyclohexane (trace 5).

The fluorescence excitation spectra corresponding to the solutions 1-4, recorded by monitoring the
fluorescence at 380 nm, are presented in the inset (Figure 3). The basic features of all the spectra
look similar except of diminishing intensity with increase of phenol concentration, and no distinct
band shows up at wavelengths longer than 300 nm that can correspond to the 7AI-phenol complex.
Thus, in longer wavelength region (λ > 300 nm) the features of the excitation and absorption spectra
(Figure 1) are different, and this indicates again that the complex is nonfluorescent.

Materials
1. 7-Azaindole and phenol were procured.
2. UV grade methylcyclohexane
3. The spectrum of pure methylcyclohexane recorded by exciting at 300 nm.
4. The concentration of the stock solution of phenol was 2 M, and it was added gradually to the
said 7AI solution to get its effective concentration in the range of 3.33*10-3 to 3.33*10-2 M.