Sumanene-Stacked Supramolecular Polymers. Dynamic, Solvation-Directed Control

Supramolecular polymer chemistry has recently garnered considerable attention in multidisciplinary science, however, the mutual choice of supramolecular hosts and monomer units has yet to be demonstrated on a trial-and-error basis. Curved-pi-buckybowls appear to be good “seeds” for supramolecular polymers, however, the very fast bowl-to-bowl inversion in the solution hampers their wide usage. In this study, we found that a pristine buckybowl, sumanene, can form solution-state supramolecular polymers via bowl-to-bowl inversion. We also demonstrated that sumanene supramolecular polymers can be dynamically controlled by external stimuli, in which solvation plays a significant role. This study not only provides new guidelines for the rational design of supramolecular polymers, particularly for the use of buckybowls, but also presents interesting dynamic behaviors of supramolecular polymerization.