Effect of an Aromatic Solvent on Hydrogen-Bond-Directed Supramolecular Polymerization Leading to Distinct Topologies.

: Transcending phenomenon, self-assembly of synthetic molecules is now becoming an essential tool to design supramolecular materials not only in the thermodynamically stable state but also in kinetically trapped states. However, an approach to design complex self-assembly comprising different types of self-assembled states remains elusive. Herein we demonstrate an example of such systems based on our unique supramolecular polymer mediated by supermacrocyclization of hydrogen-bonding π-conjugated molecule. By adding an aromatic solvent in nonpolar solutions of monomer, spontaneous nucleation triggered by the supermacrocyclization was suppressed so that isothermal supramolecular polymerization could be achieved from kinetically formed topological variants and amorphous agglomerates to afford helicoidal structures hitherto obtainable only with very slow cooling of a hot solution. By increasing the proportion of aromatic solvent further, we could find another self-assembly path based on competing extended hydrogen-bonded motifs to afford crystalline nanowires.