Sequence-Isomerism-Controlled Macromolecular Self-Assembly in Dendritic Rod-Like Molecules

Although in Nature sequence control is widely adopted to tune the structure and functions of biomacromolecules, it remains challenging and largely unexplored in synthetic macromolecular systems due to the difficulties in a precision synthesis, which impedes the understanding of the structure-property relationship in macromolecular sequence isomerism. Herein, we report the sequence-controlled macromolecular self-assembly enabled by a pair of rationally designed isomeric dendritic rod-like molecules. With an identical chemical formula and molecular topology, the molecular solid angle of the dendron isomers was determined by the sequence of the rod building blocks tethered with side chains of different lengths. As a result, entirely different supramolecular motifs of discs and spheres were generated, which were further packed into a hexagonally packed cylinder phase and a dodecagonal quasicrystalline sphere phase, respectively. Given the efficient synthesis and modular structural variations, it is believed that the sequence-isomerism-controlled self-assembly in dendritic rod-like molecules might provide a unique avenue toward rich nanostructures in synthetic macromolecules.