（1. Key Laboratory of Polymer Chemistry & Physics of Ministry of Education, Center for Soft Matter Science and Engineering, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China） （2. Center for Advanced LowDimension Materials, State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Material Science and Engineering, Donghua University, Shanghai 201620, China）
Compared with small molecules, the properties of synthetic polymers are not sensitive to the minute difference in their primary chemical structures, but rather depend on the collective interaction among monomers. Nonetheless, biomacromolecules exhibit an extraordinary sensitivity to the fine structural differences. The gap between these two categories has been filled with the emerging “giant molecules” over the past decade. Giant molecules are precise macromolecules based on molecular nanoparticles with rigid 3D framework, including but not limited to giant surfactants, giant shape amphiphiles, giant polyhedra, and giant molecular Janus particles. Their synthesis can be facilitated by click chemistry and other highly efficient chemical transformations with excellent atom economy. It is thus possible to study the influence of minute structural differences on their final assembly and properties. This review summarizes the relevant work on the difference between various isomers of giant molecules, especially regioisomers. The molecular mechanism behind the distinct phase behaviors are thoroughly discussed, which reveals how the atomic precision on primary chemical structure dominates hierarchical assembly and how the difference propagates and gets amplified across different length scales.