The
excited-state intramolecular proton-transfer (ESIPT) process in
1,8-dihydroxyanthraquinone (18DHAQ) dye has been investigated in protic
ionic liquid (PIL) solvents using photochemical measurements. The
results demonstrate noteworthy modulations in both steady-state and
time-resolved emission characteristics of excited normal (N*) and
tautomeric (T*) forms of the dye. That the emission of T* increases
unexpectedly upon increasing solvent viscosity indicates that subsequent
to the initial forward ESIPT, there is also a relatively slower back
ESIPT process involved for the excited dye. It is inferred that the
propensity of this back ESIPT process is determined by the dynamics of
the diffusive solvent relaxation, a process that is known to be strongly
viscositydependent in ionic liquids. Evidence of both forward and back
ESIPT for the dye has been obtained from femtosecond fluorescence
up-conversion measurements. While an unusually fast forward ESIPT is
clearly observed in all of the PILs studied, the uncommon back ESIPT
process is distinctly indicated in PIL solvents having lower
viscosities, certainly due to reasonably fast diffusive solvent
relaxation in these solvents that causes a temporal modulation in the
energies of the normal and tautomeric forms within a reasonably short
time and thereby brings down the energy of N* compared to that of T*,
triggering the back ESIPT process. Observation of
solvent-viscosity-dependent back ESIPT is an intriguing finding for the
present study as to the best of our knowledge, such a behavior has so
far not been reported in the literature for the ESIPT reaction.