Work

Hierarchical Chiral Self-Assembly of Nanocylinders Composed of Sequence-Defined Mesogenic Dimers

Year: 2026

Type: article

Abstract: Chiral ensembles can arise through supramolecular curvature that resolves geometric frustrations in the packing of bent, achiral molecular or colloidal building blocks. Here, we leverage orthogonal protection-deprotection click chemistry to create sequence-defined mesogenic heterodimers exhibiting emergent chirality. We compare the hierarchical self-assembly of the synthesized asymmetric, achiral heterodimers, which differ only in the position of a methyl substituent. Both dimers form chiral spherulites composed of nanocylinders. However, the detailed arrangement of nanocylinders depends on the position of the methyl substituent and the crystallization conditions. Despite the chemical similarity, in one dimer, two crystalline forms are optically active. They form conglomerates of dextrorotatory and levorotatory spherulites. The other dimer forms more highly anisotropic spherulites that mask circular birefringence arising from the misorientation of nanocylinders, while mapping of nanocylinder directors reveals a sense at the spherulite surface. We propose that differences in nanocylinder arrangements may arise from changes in nanocylinder curvature and dimensions dictated by the methyl substituent position, inducing chirality. These results demonstrate multiscale hierarchical assembly relevant to dense systems of tubular structures and highlight the role of sequence and molecular design in directing the bottom-up hierarchical self-assembly and chirality of mesogenic systems.

Source: Journal of the American Chemical Society

DOI: 10.1021/jacs.6c05456