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 enlist<i>exo</i>-templating to mold the formation of large, multicomponent supramolecular structures. Specifically, a charged <b>ring</b>docks at 1,5-dioxynaphthalene stations within <i>exo</i>-functionalized building blocks to promote formation of cuboctahedral Pd₁₂L₂₄ nanospheres via exoskeletal templating. With <i>exo</i>-templating<b> </b><b>ring</b> 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 <i>endo</i>-templates, we demonstrate <i>exo</i>-templating is particularly suited for larger, complex self-assembled structures.