Recent Progress on Giant Molecules: Synthesis, Assembly, and Applications

Synthetic polymers, which typically rely on physical interactions between repeating units, often lack the structural precision required for controlling such hierarchical organization, thereby limiting the understanding of the formation and manipulation of complex molecular assemblies. In recent years, giant molecules developed from molecular nanoparticles have emerged as a promising candidate. Featuring well‐defined structures and controllable surface functionalities, these nanoparticles enable the precise synthesis of giant molecules through sequential click synthesis strategies. Giant molecules retain the structural precision of their small‐molecule counterparts while exhibiting significantly enlarged dimensions, bridging the gap between small molecules and traditional polymers. Their self‐assembly in both bulk and solution frequently yields highly diverse, thermodynamically stable hierarchical structures, as well as unconventional nanoscale phases, indicating the critical influence of precise primary molecular structure and assembly conditions on the resulting morphology. The expanding range of applications based on giant molecules demonstrates their value not only as model systems for investigating controlled hierarchical self‐assembly but also as versatile platforms for engineering functional nanostructures. The design concept of giant molecules offers a promising strategy for the future development of advanced functional materials with programable order across multiple length scales.