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

Nature Chemistry volume 17, pages 1067–1075 (2025)Cite this article

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Abstract

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.

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Fig. 1: Illustration of pathway complexity and the template effect.
Fig. 2: Investigation of the self-assembly of Pd12(LMeO)24 nanospheres.
Fig. 3: The formation of the nanospheres via different pathways.
Fig. 4: Exo-templated versus non-templated self-assembly of M12L24 nanosphere at 25 °C and 10 °C.
Fig. 5: Pathway switching for self-assembly of M12L24 nanosphere at 10°C.

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Data availability

The raw data generated during this study are available in the Supplementary Information. All raw data that support the findings of this study are available via Figshare at https://doi.org/10.6084/m9.figshare.28163420.v1 (ref. 85). Source data are provided with this paper.

Code availability

Input and automation codes for AMBER simulations are supplied with computational results and are available via Figshare at https://doi.org/10.6084/m9.figshare.28163420.v1 (ref. 85).

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Acknowledgements

This study was supported by the Holland Research School for Molecular Sciences (HRSMC) and the University of Amsterdam. We acknowledge the University of Amsterdam for financial support to RPA sustainable chemistry. The funders had no role in study design, data collection and analysis, decision to publish or preparation of the manuscript. We thank A. Ehlers for support performing the 1H NMR studies and E. Zuidinga for help carrying out the MS experiments.

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Author notes

  1. T. Bouwens

    Present address: Department of Chemical Engineering, Delft University of Technology, Delft, Netherlands

  2. E. O. Bobylev

    Present address: Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA, USA

  3. D. A. Poole III

    Present address: Department of Chemistry and Pharmaceutical Sciences, Vrije Universiteit Amsterdam, Amsterdam, the Netherlands

Authors and Affiliations

  1. van ‘t Hoff Institute for Molecular Sciences, Universiteit van Amsterdam, Amsterdam, the Netherlands

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

  2. AMOLF, Amsterdam, the Netherlands

    L. S. D. Antony & E. Alarcón-Lladó

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Contributions

T.B., S.M. and J.N.H.R. proposed, designed and conceptualized the research. T.B. synthesized and characterized the ligands, the macrocycle and pseudorotaxane, together with S.M. All NMR experiments were performed by T.B. supported by D.A.P. and S.M. The ESI–MS measurements were performed and analysed by T.B. and E.O.B. The MD simulations were carried out and analysed by D.A.P. The DLS and AFM experiments were performed and analysed by S.M., L.S.D.A. and E.A.-L. Remaining experiments were designed by T.B., S.M. and J.N.H.R. Funding acquisition was by T.B. and J.N.H.R. and project administration was realized by T.B. and S.M. The supervisors during this project were S.M., E.A.-L. and J.N.H.R. The manuscript was prepared by T.B., S.M. and J.N.H.R. and revised with the input of all authors.

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Correspondence to J. N. H. Reek.

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Methods, experimental details, Supplementary Figs. 1–40 and Tables 1–5.

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Source data NMR and MS.

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Source data DLS and AFM.

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Bouwens, T., Bobylev, E.O., Antony, L.S.D. et al. Exo-templating via pseudorotaxane formation reduces pathway complexity in the multicomponent self-assembly of M12L24 nanospheres. Nat. Chem. 17, 1067–1075 (2025). https://doi.org/10.1038/s41557-025-01808-w

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