Amplification of Molecular Asymmetry during the Hierarchical Self-Assembly of Foldable Azobenzene Dyads into Nanotoroids and Nanotubes

The amplification of molecular asymmetry through self-assembly is a phenomenon that not only comprehends the origin of homochirality in nature but also produces chiroptically active functional materials from molecules with minimal enantiomeric purity. Understanding how molecular asymmetry can be transferred and amplified into higher-order structures in a hierarchical self-assembly system is important but still unexplored. Herein, we present an intriguing example of the amplification of molecular asymmetry in hierarchically self-assembled nanotubes that feature discrete and isolatable toroidal intermediates. The hierarchical self-assembly is initiated via asymmetric intramolecular folding of scissor-shaped azobenzene dyads furnished with chiral side chains. When scalemic mixtures of the enantiomers are dissolved in a non-polar solvent and cooled to 20 °C, single-handed nanotoroids are formed, as confirmed using atomic force microscopy and circular dichroism analyses. A strong majority-rules effect at the nanotoroid level is observed and can be explained by a low mismatch penalty and a high helix-reversal penalty. The single-handed nanotoroids stack upon cooling to 0 °C to exclusively afford their respective single-handed nanotubes. Thus, the same degree of amplification of molecular asymmetry is realized at the nanotube level. The internal packing efficiency of molecules within nanotubes prepared from the pure enantiomers or their scalemic mixtures is likely different, as suggested by the absence of higher-order structure (supercoil) formation in the latter. X-ray diffraction analysis of the anisotropically oriented nanotube films revealed looser molecular packing within the scalemic nanotubes, which clearly reflects the lower enantiomeric purity of their internal chiral side chains.