Dynamic stokes shift and excitation wavelength dependent fluorescence of dipolar molecules in room temperature ionic liquids

Abstract

Room temperature ionic liquids (RTILs) are viscous media consisting entirely of ions. Because of the complex nature of various interactions in these media, the solvent properties of the RTILs are very little understood. Since the fluorescence response of molecules comprising conjugated electron donor and acceptor groups, referred to as dipolar molecules, is one of the most frequently exploited sources of information on complex media, whose properties are largely unknown, it is possible to obtain insight into the structure and dynamics of the RTILs by studying the fluorescence behavior of dipolar solutes in these complex media. The most commonly exploited utility of a fluorescent dipolar system is in the estimation of the polarity of the media from its steady state fluorescence response. While several dipolar systems do provide estimates of the polarity of various RTILs, there can be circumstances when the steady state emission frequency of a dipolar system may not truly reflect the equilibrium solvation energy and, hence, the polarity of the medium. The fluorescence response of a dipolar system can be dependent on the excitation wavelength, an observation not commonly encountered in conventional solvents of similar polarities. On the other hand, the time-resolved fluorescence behavior of a dipolar solute in polar medium is one of the primary sources of information on the time-scale of reorganization of the solvent molecules around the photoexcited species. As the RTILs are sufficiently polar media, the time-dependent fluorescence data of the dipolar systems provide insight into the dynamics and mechanism of solvation in these media, which differ considerably from the conventional solvents. These aspects have been discussed taking into consideration the inherent absorption and fluorescence behavior of the imidazolium ionic liquids.