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<p>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 mould the formation of large, multicomponent supramolecular structures. Specifically, a charged ring docks at 1,5-dioxynaphthalene stations within <i>exo</i>-functionalized building blocks to promote formation of cuboctahedral Pd<sub>12</sub>L<sub>24</sub> nanospheres via exoskeletal templating. With the <i>exo</i>-templating ring present, nanosphere formation occurs via small Pd<sub><i>x</i></sub>–L<sub><i>y</i></sub> oligomers, while in the absence of the ring a Pd<sub><i>x</i></sub>–L<sub><i>y</i></sub> 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 that <i>exo</i>-templating is particularly suited for larger, complex, self-assembled structures.</p><p></p>

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Exo-templating via pseudorotaxane formation reduces pathway complexity in the multicomponent self-assembly of M12L24 nanospheres

  • 期刊论文

  • 发表日期：

    2025年5月12日

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  • T. Bouwens,
  • E. O. Bobylev,
  • L. S. D. Antony,
  • D. A. Poole III,
  • E. Alarcón-Lladó,
  • S. Mathew,
  • J. N. H. Reek

摘要

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 exo-templating to mould the formation of large, multicomponent supramolecular structures. Specifically, a charged ring docks at 1,5-dioxynaphthalene stations within exo-functionalized building blocks to promote formation of cuboctahedral Pd12L24 nanospheres via exoskeletal templating. With the exo-templating ring present, nanosphere formation occurs via small Pdx–Ly oligomers, while in the absence of the ring a Pdx–Ly 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 that exo-templating is particularly suited for larger, complex, self-assembled structures.