A Computational and Spectroscopic Analysis of Solvate Ionic Liquids Containing Anions with Long and Short...

Anion-driven, nanoscale polar-apolar structural organization is investigated in a solvate ionic liquid (SIL) setting by comparing sulfonate-based anions with long and short perfluorinated alkyl chains. Representative SILs are created from 1,2-bis(2-methoxyethoxy)ethane ("triglyme" or "G3"), lithium nonafluoro-1-butanesulfonate, and lithium trifluoromethanesulfonate. Molecular dynamics simulations, density functional theory computations, and vibrational spectroscopy provide insight into the overall liquid structure, cation-solvent interactions, and cation-anion association. Significant competition between G3 and anions for cation-binding sites characterizes the G3-LiC₄F₉SO₃ mixtures. Only 50% of coordinating G3 molecules form tetradentate complexes with Li⁺ in [(G3)₁Li][C₄F₉SO₃]. Moreover, the SIL is characterized by extensive amounts of ion pairing. Based on these observations, [(G3)₁Li][C₄F₉SO₃] is classified as a "poor" SIL, similar to the analogous [(G3)₁Li][CF₃SO₃] system. Even though the comparable basicity of the CF₃SO₃^- and C₄F₉SO₃^- anions leads to similar SIL classifications, the hydrophobic fluorobutyl groups support extensive apolar domain formation. These apolar moieties permeate throughout [(G3)₁Li][C₄F₉SO₃] and persist even at relatively low dilution ratios of [(G3)₁₀Li][C₄F₉SO₃]. By way of comparison, the CF₃ group is far too short to sustain polar-apolar segregation. This demonstrates how chemically modifying the anions to include hydrophobic groups can impart unique nanoscale organization to a SIL. Moreover, tuning these nano-segregated fluorinated domains could, in principle, control the presence of dimensionally ordered states in these mixtures without changing the coordination of the lithium ions.