NCHEM-22122509B_Reeketal_FIGSHARE.rar

Selective formation of multicomponent structures via the self-assembly of numerous building blocks is ubiquitous in biological systems but challenging to emulate synthetically. More components introduce additional possibilities for kinetic intermediates with trap-state ability, hampering access to desired products. In covalent chemistry, templates, reagents and catalysts are applied to create alternative pathways for desired product formation. Analogously, we enlistexo-templating to mold the formation of large, multicomponent supramolecular structures. Specifically, a charged ringdocks at 1,5-dioxynaphthalene stations within exo-functionalized building blocks to promote formation of cuboctahedral Pd₁₂L₂₄ nanospheres via exoskeletal templating. With exo-templating ring present, nanosphere formation occurs via small Pd_x–L_y oligomers, while in absence a Pd_x–L_y polymer resting-state rapidly evolves, from which nanosphere formation occurs slowly. We demonstrate a form of kinetic templating—via intermediate destabilization—resembling properties observed in catalysis. Importantly, unlike typically employed endo-templates, we demonstrate exo-templating is particularly suited for larger, complex self-assembled structures.