Achiral Solvent Inversed Helical Pathway and Cosolvent Controlled Excited‐State “Majority Rule” in Enantiomeric Dansulfonamide Assemblies

Abstract

AbstractAchiral solvents are commonly utilized to induce the self‐assembly of chiral molecules. This study demonstrates that achiral solvents can trigger helicity inversion in the assemblies of dansyl amphiphiles and control the excited‐state “majority rule” in assemblies composed of pure enantiomers, through variation of the cosolvent ratio. Specifically, enantiomers of dansyl amphiphiles self‐assemble into helical structures with opposite handedness in methanol (MeOH) and acetonitrile (MeCN), together with inversed circular dichroism and circularly polarized luminescence (CPL) signals. When a mixture of MeOH and MeCN is employed, the achiral cosolvents collectively affect the CPL of the assemblies in a way similar to that of “mixed enantiomers”. The dominant cosolvent governs the CPL signal. As the cosolvent composition shifts from pure MeCN to MeOH, the CPL signals undergo a significant inversion and amplification, with two maxima observed at ≈20% MeOH and 20% MeCN. This study deepens the comprehension of how achiral solvents modulate helical nanostructures and their excited‐state chiroptical properties.