Cogwheel Mechanism of Helical Self-Organization is Thermodynamically Controlled, Self-Repairing, and Universal.

ABSTRACT

The cogwheel mechanism of helical self-organization, reported by us, generates columns with the alkyl chains of their components parallel to the column axis. This mechanism disregards the enantiomeric purity of constituents and, under suitable design, provides the fastest rate of helical self-organization. Here, we investigate the supramolecular structure of a thermodynamically controlled helical self-organization system. Unexpectedly, we found that this system follows a cogwheel mechanism of helical self-organization that does not contain the two key parameters of the cogwheel mechanism the length of the alkyl group of the self-assembling dendron identical to the helical half-pitch (hhp) of the column and the presence of chiral branches pointing toward the column center. Unpredictably, we uncovered that the presence of chiral branching points and strict alkyl chain lengths is not a requirement of the cogwheel mechanism. A self-repairing process provides access to a constant hhp via a shorter and longer alkyl chain length than the originally exact demanded value, which together with the lack of branching point(s) demonstrates the universality of the cogwheel mechanism of helical self-organization. Applications derived from this concept are envisioned.