Control over the Aspect Ratio of Supramolecular Nanosheets by Molecular Design

Recent developments in kinetically controlled supramolecular polymerization permit control of the size (i.e., length and area) of self‐assembled nanostructures. However, control of molecular self‐assembly at a level comparable with organic synthetic chemistry and the achievement of structural complexity at a hierarchy larger than the molecular level remain challenging. This study focuses on controlling the aspect ratio of supramolecular nanosheets. A systematic understanding of the relationship between the monomer structure and the self‐assembly energy landscape has derived a new monomer capable of forming supramolecular nanosheets. With this monomer in hand, the aspect ratio of a supramolecular nanosheet is demonstrated that it can be controlled by modulating intermolecular interactions in two dimensions. Design on a small scale! Molecular self‐assembly in solution, with rational molecular design and under kinetic control, has achieved supramolecular nanosheets with controlled area and aspect ratio.