Spontaneous hierarchical assembly of crown ether-like macrocycles into nanofibers and microfibers induced by alkali-metal and ammonium salts

Schiff base macrocycle 1, which has a crown ether like central pore, was combined with different alkali-metal and ammonium salts in chloroform, resulting in one-dimensional supramolecular aggregates. The ion-induced self-assembly was studied with solid-state NMR spectroscopy, transmission electron microscopy (TEM), scanning electron microscopy (SEM), and atomic force microscopy (AFM). It was found that the lengths and widths of the superstructures depend on the cation and counteranion of the salts. Among the salts being used, Na⁺ and NH₄ ⁺ ions with BF₄ ^- ions showed the most impressive fibrous structures that can grow up to 1 mm in diameter and hundreds of microns in length. In addition, the size of the fibers can be controlled by the evaporation rate of the solvent. A new macrocycle with bulky triptycenyl substituents that prevent supramolecular assembly was prepared and did not display any nanofibers with alkali-metal ions in chloroform when studied with TEM.