6533b872fe1ef96bd12d380c

RESEARCH PRODUCT

Flipping Motion To Bias the Organized Supramolecular Polymerization of N-Heterotriangulenes

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Synergistic experimental and theoretical studies have allowed the disentangling of the possible pathways for the supramolecular polymerization of a series of dicyanovinyl-bridged N-heterotriangulene (NHT) derivatives bearing benzamide units with achiral (1a) and chiral (1b,c) side chains. The synthesis of these bowl-shaped, self-assembling units yields a mixture of monomeric species with C3- and C1-symmetry. Both monomeric species are able to self-assemble into different supramolecular aggregates with sufficient stability to coexist in freshly prepared solutions. The dissimilar ratio of the aggregates initially generated results in different spectroscopic features and, more specifically, in the apparition of nonmirror circular dichroism (CD) spectra for chiral 1b and 1c. The interconversion at room temperature of the aggregates formed by the C3- and C1-symmetry monomeric species is energetically unfavorable due to the steric hindrance between the neighboring dicyanovinyl groups within the aggregate. Heati...