What type of nanoscopic environment does a cationic fluorophore experience in room temperature ionic liquids?

Abstract

In the presence of a cationic fluorophore (rhodamine 6G) whose absorption has a significant spectral overlap with the emission of a room temperature ionic liquid (RTIL), the emission of the latter gets quenched, and the quenching has been shown to be dynamic in nature. It has been shown that resonance energy transfer (RET) indeed happens between the RTIL (donor) and rhodamine 6G (cationic acceptor), and RET is the reason for the quenching of the RTIL emission. The spectral and temporal aspects of the RET (between neat RTILs as the donors and rhodamine 6G as the acceptor) were closely studied by steady-state and picosecond time-resolved fluorescence spectroscopy. The influence of the alkyl chain length of the cation, size of the anion, excitation wavelength and concentration of the acceptor on the RET dynamics were also investigated. The energy transfer time (obtained from the rise time of the acceptor) was noted to vary from 2.5 ns to 4.1 ns. By employing the Förster formulation, the donor–acceptor distance was obtained, and its magnitude was found to vary between 31.8 and 37.1 Å. The magnitude of the donor–acceptor distance was shown to be independent of the alkyl chain length of the cation but dependent on the size of the anion of the RTIL. Moreover, the donor–acceptor distance was observed to be independent of the excitation wavelength or concentration of the acceptor. It was shown that the Förster formulation can possibly account for the mechanism and hence can explain the experimental observables in the RET phenomenon. Following the detailed experiments and rigorous analysis, a model has been put forward, which can successfully explain the nanoscopic environment that a cationic fluorophore experiences in an RTIL. Moreover, the nanoscopic environment experienced by the cationic probe has been noted to be different from that experienced by a neutral fluorophore.