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

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 beta-DCS or a photopolymerizable PCDA. Fast cooling leads to the co-assembled PAG/beta-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. Pathway-dependent supramolecular assemblies from a rationally designed glutamide derivative were found, which formed distinct chiral nanotwist and nanotube depending on the cooling rate. Pathway-dependent self-assembly showed also the ability to control over the guest molecules with emergent blue or green circularly polarized luminescence and topochemical polymerization.image