Temperature-Controlled, Reversible, Nanofiber Assembly from an Amphiphilic Macrocycle

One-dimensional nanostructures are self-assembled from an amphiphilic arylene-ethynylene macrocycle (AEM) in solution phase. The morphology and size of the nanostructures are controlled by simply changing the temperature, reversibly switching between monomolecular cross-sectioned nanofibers and large bundles. At elevated temperature in aqueous solutions, the tri(ethylene glycol) (Tg) side chains of the AEM become effectively more hydrophobic, thus facilitating intermolecular association through side chain interactions. The enhanced intermolecular association causes the ultrathin nanofibers to be bundled, forming an opaque dispersion in solution. The reported observation provides a simple molecular design rule that may be applicable to other macrocycle molecules for use in temperature-controlled assembly regarding both size and morphology.