Structural analysis of ionic liquids with symmetric and asymmetric fluorinated anions

Ionic liquids (ILs) with relatively low viscosities and broad windows of electrochemical stability are often constructed by pairing asymmetric cations with bisfluorosulfonylimide (FSI^-) or bistriflimide (NTf₂ ^-) anions. In this work, we systematically studied the structures of ILs with these anions and related perfluorobis-sulfonylimide anions with asymmetry and/or longer chains: (fluorosulfonyl)(trifluoromethylsulfonyl)imide (BSI_0,1 ^-), bis(pentafluoroethylsulfonyl)imide (BETI^-), and (trifluoromethylsulfonyl) (nonafluorobutylsulfonyl)imide (BSI_1,4 ^-) using high energy X-ray scattering and molecular dynamics simulation methods. 1-alkyl-3-methylimidazolium cations with shorter (ethyl, Im_2,1 ⁺) and longer (octyl, Im_1,8 ⁺) hydrocarbon chains were selected to examine how the sizes of nonpolar hydrocarbon and fluorous chains affect IL structures and properties. In comparison with these, we also computationally explored the structure of ionic liquids with anions having longer fluorinated tails.