Enantiopure Laterally Functionalized Alleno-Acetylenic Macrocycles: Synthesis, Chiroptical Properties, and Self-Assembly in Aqueous Media

A family of shape‐persistent alleno–acetylenic macrocycles (SPAAMs), peripherally decorated with structurally diverse pendant groups, has been synthesized and characterized in enantiomerically pure form. Their electronic circular dichroism (ECD) spectra feature a strong chiroptical response, which is more than two times higher than for open‐chain tetrameric analogues. A water‐soluble oligo(ethylene glycol)‐appended SPAAM undergoes self‐assembly in aqueous solution. Morphology studies by cryogenic transmission electron microscopy (cryo‐TEM) revealed the formation of aggregates with fibrous fine structures that correspond to tubular, macrocyclic stacks. Decorating macrocycles! A family of shape‐persistent alleno–acetylenic macrocycles (SPAAMs), peripherally decorated with structurally diverse pendant groups, has been synthesized in enantiomerically pure form. Their electronic circular dichroism spectra feature a strong chiroptical response, which is not reduced by large achiral peripheral substituents. The first optically active, water‐soluble oligo(ethylene glycol) (OEG)‐appended SPAAMs were prepared and further characterized by cryo‐TEM, revealing the formation of aggregates with fibrous fine structures that correspond to tubular, macrocyclic stacks.