Nanoscale Aggregates as Building Elements in a Biomimetic Living Self-Assembly

In this work, we report on a complex dynamic supramolecular assembly pathway for a perylene diimide (PDI) derivative; this pathway involves the sequential formation of three kinetically trapped assemblies (i.e., from smooth nanospheres to microspheres to nanofiber microspheres) and thermodynamically stable microribbons. Interestingly, the stable nuclei, which are formed via the fusion of densely entangled nanofibers on the microspheres, enabled the direct anchoring of nanospheres at the termini for the growth of microribbons. Furthermore, we demonstrate the living nature of this system by observing the direct terminal growth of nanospheres on added microribbon seeds under identical self-assembly conditions. Our findings represent a significant step toward artificial systems that are capable of resembling biological systems.