Direct Observation and Manipulation of Supramolecular Polymerization by High‐Speed Atomic Force Microscopy

Abstract Despite recent advances in mechanistic understanding and controlled‐synthesis methodologies regarding synthetic supramolecular assemblies, it has remained challenging to capture the molecular‐level phenomena in real time, thus hindering further progress in this research field. In this study, we applied high‐speed atomic‐force microscopy (AFM), which has extraordinary spatiotemporal resolution (1 nm and sub‐100 ms), to capture dynamic events occurring during synthetic molecular self‐assembly. High‐speed AFM permitted the visualization of unique dynamic behavior, such as seeded growth and self‐repair in real time. Furthermore, scanning‐probe AFM permitted the site‐specific manipulation and functionalization of a molecular self‐assembly. This powerful combination of bottom‐up and top‐down approaches at the molecular level should enable targeted syntheses of unprecedented functional nanoarchitectures.