Within the [Li][NTf 2 ] mole fraction range of 0.4 to 0.5, we mostly find one-fold G3coordinated cations where the G3 coordinates cations with all four oxygen atoms, resulting in crown-ether-like chelate complexes. However, additional oxygen coordination is provided by one adjacent [NTf 2 ] -anion. Here, almost all G3 molecules are involved in coordinating the cations. These mixtures exhibit D [Li] + /D G3 ra-tios near unity, supporting the formation of stable, long-lived [Li] + -G3 complexes, concertedly moving as a joint unit. According to the criteria introduced by Ueno et al., they can indeed be referred to as SIL candidates.