<i>n</i>-Perfluorooctane versus <i>n</i>-Octane: Pyrene Fluorescence to Compare and Contrast Solute Solvation

Fluorous solvents may offer distinctly different solvation environments to a solute compared to their hydrocarbon analogues due to the inherently high electronegativity associated with fluorine. Solute solvation within <i>n</i>-perfluorooctane (PFO) is compared with that in <i>n</i>-octane using the well-established polycyclic aromatic hydrocarbon (PAH) fluorescence probe pyrene in the temperature range of 288 to 318 K. Both density (<i>ρ</i>) and dynamic viscosity (<i>η</i>) of PFO are considerably higher than those of <i>n</i>-octane. UV-vis molecular absorbance, fluorescence emission/excitation, and excited-state emission intensity decay reveal the cybotactic region of pyrene to be more nonpolar in PFO than that in <i>n</i>-octane. Bimolecular quenching rate constants (<i>k</i>_q) for the pyrene-nitrobenzene fluorophore-quencher pair adhere to the Stokes-Einstein formulation; however, they are considerably higher than the estimated rate constants for the diffusion-controlled process (<i>k</i>_diff). This is due to the high electron affinity of nitrobenzene leading to aromatic π-π interactions between pyrene and nitrobenzene. For a nonaromatic low electron affinity quencher, such as nitromethane, while <i>k</i>_q < <i>k</i>_diff in <i>n</i>-octane, <i>k</i>_q > <i>k</i>_diff in PFO. This is due to the fact that highly electronegative fluorines on PFO stabilize the partial positive charge (δ⁺) that develops on excited pyrene during electron/charge transfer to the quencher nitromethane, facilitating quenching in the process. Exciplex formation between pyrene and triethylamine (TEA) is more favored in PFO as opposed to <i>n</i>-octane although <i>η</i>_PFO > <i>η</i>_{<i>n-</i>octane.} The developing charge on the exciplex is stabilized by the electronegative fluorines of the PFO. The pyrene-TEA exciplex appears to form exclusively in the excited state of pyrene, and the kinetics of exciplex formation is in the subnanosecond regime. On the contrary, the efficiency of exciplex formation between pyrene and <i>N</i>,<i>N</i>-dimethylaniline (DMA) is comparable in PFO and <i>n</i>-octane, and the kinetics is slower in comparison to that of the pyrene-TEA exciplex. Certain ground-state heterogeneity is detected for the pyrene-DMA system in PFO due to the low solubilizing ability of the fluorous solvent. Highly electronegative fluorines on perfluorohydrocarbon solvents are found to offer unusual and unique solvation characteristics.