Pathway‐Dependent Self‐Assembly for Control over Helical Nanostructures and Topochemical Photopolymerization

Abstract Pathway‐dependent self‐assembly, in which a single building block forms two or more types of self‐assembled nanostructures, is an important topic due to its mimic to the complexity in biology and manipulation of diverse supramolecular materials. Here, we report a pathway‐dependent self‐assembly using chiral glutamide derivatives ( L or D ‐PAG), which form chiral nanotwist and nanotube through a cooperative slow cooling and an isodesmic fast cooling process, respectively. Furthermore, pathway‐dependent self‐assembly can be harnessed to control over the supramolecular co‐assembly of PAG with a luminophore β ‐DCS or a photopolymerizable PCDA. Fast cooling leads to the co‐assembled PAG/ β ‐DCS nanotube exhibiting green circularly polarized luminescence (CPL), while slow cooling to nanofiber with blue CPL. Additionally, fast cooling process promotes the photopolymerization of PCDA into a red chiral polymer, whereas slow cooling inhibits the polymerization. This work not only demonstrates the pathway‐dependent control over structural characteristics but also highlights the diverse functions emerged from the different assemblies.