Inherently chiral media

Ionic liquids ILs are molecular salts with low melting points (even liquid at room T, RTILs), with attractive properties as media for chemical processes and particularly electrochemical ones, for which they act as both solvent and supporting electrolyte and feature an extremely well structured, stable structure at the interphase with a charged electrode, resembling a semisolid crystal or a bulk liquid crystal, extending for many layers, standing also in the presence of water traces, and possibly being tunable by the presence of in-situ present additives.

Thus chiral ionic liquids CILs (many of which have been so far proposed, although in electrochemistry they are surprisingly still nearly unexplored) should be more effective in trasmitting the chiral information respect to chiral organic solvents or chiral supporting electrolytes. Moreover, considering the outcome of the parallel experiments on inherently chiral electrodes, the best results should come from inherently chiral ionic liquids ICILs.

Enantiopure ICILs with inherently chiral dications have been recently developed by dialkylating with suitably long chains enantiopure inherently chiral bicollidine scaffolds (previously separated by fractional crystallization as diastereomeric salts), and combining them with bistriflimide anions.

Different chiral probes are very nicely discriminated in terms of potential difference working on achiral electrode and either (a) in bulk ICIL (a drop on screen printed electrode supports) or (b) in achiral IL but in the presence of ICIL as additive.

Enantiodiscrimination CV tests on (R)- and (S)-ferrocenyl antipodes on screen printed electrodes in (BMIM)PF6 (gray), or with addition of 0.01 M (R) or (S) enantiopure antipodes (green or red lines, respectively) of an inherently chiral additive

Since the application as additive does not require to be liquid, similar effects can be advantageously observed using as additive a smaller member of the same family, with shorter chains and higher melting point, but of much faster and easy preparation; and even using uncharged helicene-based additives. The probe enantiomer potential differences appear to increase linearly with the logarythm of the additive concentration.

To explain such fascinating observations we are evaluating the intrinsic very high local order of an ionic liquid at a charged interphase, resembling bulk liquid crystal properties, which could be similarly modulated by the addition of a chiral additive. Some local selector/probe interaction cannot be excluded, too.

We are also considering a fascinating third possible explanation, common to both approaches, inspired from a recently observed groundbreaking phenomenon , which we hope to be able to soon communicate.