Beyond Solid Chiral Electrodes: Pervasive Enantioselection in Achiral Ionic Liquids Doped With Soluble Thiahelicenes

Although inherently chiral selectors are successfully used as modified solid electrodes, homogeneously doped chiral ionic liquids for analytical sensing remain largely unexplored. Herein, we present inherently chiral mono and disubstituted alkyltetrathia[7]helicene derivatives as uncharged additives dissolved in the achiral commercial ionic liquid 1‐butyl‐3‐methylimidazolium bis(trifluoromethylsulfonyl)imide ([BMIM][TFSI]). Unlike unsubstituted thiahelicenes that undergo oxidative electrooligomerization to form solid films, adding aliphatic chains improves monomer solubility and sterically prevents film formation. The capacity of these molecules to induce a pervasive chiral environment was macroscopically validated by a high helical twisting power in nematic liquid crystals. At the electrochemical interface, enantiopure (+)‐( P )‐ and (−)‐( M )‐7,8‐dipropyltetrathia[7]helicenes acted as soluble chiral inductors. Voltammetry using ( R )‐ and ( S )‐ N , N ‐dimethyl‐1‐ferrocenylethylamine probes demonstrated unprecedented enantiodiscrimination, yielding a substantial thermodynamic peak potential separation (Δ E > 200 mV). Preliminary validation with the individual enantiomers of the pharmaceutical drug lansoprazole provided initial evidence of thermodynamic recognition beyond standard model probes. Differential pulse voltammetry on disposable screen‐printed electrodes allowed precise enantiomeric excess evaluation with strict linear correlation ( R 2 > 0.992), high sensitivity, and high reproducibility (RSD < 3.8%). This homogeneous setup overcomes the historical fouling of solid electrodes, providing a robust, time‐efficient, and fouling‐free platform for solution‐phase chiral analysis.