Anomalous Fluorescence Quenching in Fluorous Solvent-Added Media

Due to the inherent high electronegativity of fluorine, perfluorocarbons have the potential to exhibit unusual characteristics. Fluorous solvents, in this context, may afford an anomalous solubilizing behavior compared to their hydrocarbon analogues. Addition of perfluorodecalin (PFD) to <i>n</i>-hexane results in unusual fluorescence quenching of polycyclic aromatic hydrocarbons (PAHs) by the quencher nitromethane. As more viscous PFD is added to less viscous <i>n</i>-hexane, the dynamic viscosity (η) of the media increases. The bimolecular quenching rate constants (<i>k</i>_q) of the PAHs, instead of decreasing, increase as PFD is added to <i>n</i>-hexane until an equimolar mixture composition is obtained; <i>k</i>_q exhibits an expected decrease only in the PFD-rich region of the mixture. The expected decrease in <i>k</i>_q in the hydrocarbon analogue decalin added to <i>n</i>-hexane is observed across all compositions. It is proposed that highly electronegative fluorines on PFD stabilize the partial positive charge (δ⁺) that develops on excited PAHs during electron/charge transfer to the quencher nitromethane, facilitating quenching in the process. In the PFD-rich region, however, increased η starts to dominate the quenching, resulting in the expected decrease in <i>k</i>_q. A monotonic decrease in <i>k</i>_q is observed in the PFD-added <i>n</i>-hexane system for fluoranthene quenching by triethylamine (TEA) as TEA acts as the electron/charge donor and a partial negative charge (δ^-) develops on excited fluoranthene during the quenching process. No such stabilization by PFD is observed when nitrobenzene is employed as the quencher. This is attributed to the significantly higher quenching (<i>K</i>_S > 10⁴ M^-1) of PAH fluorescence by nitrobenzene due to the presence of aromatic π-π interactions between PAH and nitrobenzene, further facilitated by the higher electron affinity of nitrobenzene as compared to nitromethane. The role of fluorous media in facilitating electron/charge transfer processes is clearly established.