Room-temperature ionic liquids, particularly those based on substituted imidazolium cations, are currently being extensively studied for a variety of applications. Herein, we explore the suitability of several imidazolium salts in optical applications by carefully examining the electronic absorption and fluorescence behavior of these substances, generally believed to be transparent in most of the UV region and fully transparent in the visible region. It is shown that all imidazolium ionic liquids are characterized by significant absorption in the entire UV region and a long absorption tail that extends into the visible region. These absorption characteristics are attributed to the imidazolium moiety and its various associated structures. When excited in the UV or early part of the visible region, these liquids exhibit fluorescence, which covers a large part of the visible region and shows dramatic excitation wavelength dependence. The excitation wavelength dependent shift of the fluorescence maximum has been rationalized taking into consideration the existence of the various associated structures of the ionic liquids and the inefficiency of the excitation energy-transfer process between them. The results imply that these liquids may have serious drawbacks in some of the optical studies.

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Steady-state and time-resolved fluorescence behaviors of two dipolar solutes, coumarin 153 and 4-aminophthalimide, have been studied in an alcohol-functionalized room-temperature ionic liquid, 1-(hydroxyethyl)-3-methylimidazolium bis(trifluoromethanesulfonyl)imide. The steady-state fluorescence parameters have been exploited for the estimation of the polarity of this ionic liquid and to obtain information on the hydrogen bonding interaction between the ionic liquid and the probe molecules. The time-resolved measurements have been focused on the dynamics of solvation by studying the dynamic Stokes shift in the ps-ns time scale and solute rotation by measuring the time dependence of the fluorescence anisotropy. The time-resolved anisotropy studies reveal a significant slow down of the rotational motion of one of the probe molecules. The time-dependent fluorescence Stokes shift measurements suggest that the time-resolvable part of the dynamics is biphasic in nature, highly dependent on the probe molecule and the ultrafast component is comparatively less than that in other ionic liquids. The influence of the hydrogen bonding interaction between the probe molecules and the ionic liquids on the solute rotation and the various components of the solvation dynamics is carefully analyzed in an attempt to obtain further insight into the mechanism of solvation in these novel media.

A detailed study of the photoinduced electron transfer (PET) reaction between pyrene and N,N-dimethylaniline has been made in four different room temperature ionic liquids (ILs) using steady state and time-resolved fluorescence and laser flash photolysis techniques. Unlike that in the conventional media, no exciplex emission for this well-known system could be observed in ILs. The rate constants for the PET induced quenching of the fluorescent state of pyrene, which lie between 6.9 and 37 x 107 M-1 s-1 depending on the viscosity, are found to be 2-4 times higher than the diffusion-controlled rates in ILs. The primary photoproducts of the PET process have been characterized by transient absorption spectroscopy, and the yields of the solvent-separated PET products have been determined. Even in the least viscous IL, [emim][Tf2N], the yield of the solvent-separated radical ion is estimated to be only 0.015 +/- 0.005. In more viscous ILs such as [bmim][PF6], the yield is found to be so low that absorption due to these species could not be observed. The rate constant for the escape of the ionic products from the geminate ion pair in ILs has been estimated to be nearly 2-3 orders of magnitude lower than the back electron transfer rate. However, the small fraction of the PET products, which manage to escape geminate recombination, have been found to survive much longer compared to those in less viscous conventional solvents.

The fluorescence efficiency of a well-known microviscosity probe, 9-(dicyanovinyl)julolidine (DCVJ), which is highly sensitive to the viscosity of the medium, has been studied in seven imidazolium ionic liquids (ILs) of varying viscosities over a temperature range of 10-60 degrees C. The microviscosities around the probe in different ILs have been estimated from the linear dependence of the logarithm of fluorescence quantum yield (log phi(f)) on the logarithm of the bulk viscosity (log eta) in various conventional solvents of different viscosities at room temperature. These microviscosities, which represent the local environments around the probe, are found to be significantly different from the directly measured bulk viscosities of these ILs. The log phi(f) vs log (eta/T) plots, which are also expected to be linear, interestingly show a bilinear behavior in more viscous ILs with a break around 28-30 degrees C. The observation of a similar break in the Arrhenius plots of the rate constant of the internal rotation in DCVJ and absence of any such break in the temperature dependence of the mobility of the ILs allow us to determine the important role of the free volume around the probe in dictating the nonradiative deactivation rate or the fluorescence efficiency of DCVJ. The break in the plots, which implies a change in the available free volume around the probe at approximately 28-30 degrees C, presumably arises from the repositioning of the probe from one environment to a different one of these microheterogeneous ILs with change of temperature.