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Non-statistical assembly of multicomponent [Pd2ABCD] cages

Nature Chemistry volume 16, pages 584–591 (2024)Cite this article

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Abstract

Self-assembled hosts, inspired by biological receptors and catalysts, show application potential in sustainable synthesis, energy conversion and medicine. Implementing multiple functionalities in the form of distinguishable building blocks, however, is difficult without risking narcissistic self-sorting or a statistical mess. Here we report a systematic series of integratively self-assembled heteroleptic cages in which two square-planar PdII cations are bridged by four different bis-pyridyl ligands, A, B, C and D, via synergistic effects to exclusively form a single isomer—the lantern-shaped cage [Pd2ABCD]. This self-sorting goal—forming just one out of 55 possible structures—is reached under full thermodynamic control and can be realized progressively (by combining progenitors, such as [Pd2A2C2] with [Pd2B2D2]), directly from ligands and PdII cations or by mixing all four corresponding homoleptic cages. The rational design of complex multicomponent assemblies that enables the modular incorporation of diverse chemical moieties will advance their applicability in functional nanosystems.

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Fig. 1: Self-assembly of heteroleptic multicomponent cage [Pd2ABCD]4+ from four chemically different ligands.
Fig. 2: X-ray crystal structures of heteroleptic multicomponent cages with two or three different ligands.
Fig. 3: Characterization of heteroleptic multicomponent cage [Pd2ABCD]4+.
Fig. 4: Possible cage isomers and comparison of crystal structures of [Pd2ABCD] and [Pd2ABD4C].
Fig. 5: Thermodynamic analysis of cage isomers, competition experiments and sequential formation of [Pd2ABCD].

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Data availability

Crystallographic data for the structures reported in this paper have been deposited at the Cambridge Crystallographic Data Centre (CCDC) under the deposition numbers 2207621, trans-[Pd2A2B2](BF4)4; 2285849, [Pd2B2CD1](BF4)4; 2207623, [Pd2A2CD](BF4)4; 2285847, [Pd2B2D4C](BF4)4; 2285846, [Pd2ABCD](BF4)4; 2207626, [Pd2AB0CD](BF4)4; 2207627, [Pd2ABD4C](BF4)4; 2207628, [Pd2ABD2D](BF4)4; and 2285848, [Pd2ABCD2](BF4)4. Copies of these data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif. All other data supporting the findings of this study are available within the Article and its Supplementary Information, or from the corresponding author upon reasonable request. Source data are provided with this paper.

References

  1. Kelly, J. A., Sielecki, A. R., Sykes, B. D., James, M. N. G. & Phillips, D. C. X-ray crystallography of the binding of the bacterial cell wall trisaccharide NAM-NAG-NAM to lysozyme. Nature 282, 875–878 (1979).

    Article  CAS  PubMed  Google Scholar 

  2. Ringe, D. & Petsko, G. A. How enzymes work. Science 320, 1428–1429 (2008).

    Article  CAS  PubMed  Google Scholar 

  3. Liu, M. et al. Barely porous organic cages for hydrogen isotope separation. Science 366, 613–620 (2019).

    Article  CAS  PubMed  Google Scholar 

  4. Cook, T. R. & Stang, P. J. Recent developments in the preparation and chemistry of metallacycles and metallacages via coordination. Chem. Rev. 115, 7001–7045 (2015).

    Article  CAS  PubMed  Google Scholar 

  5. Fujita, M. et al. Self-assembly of ten molecules into nanometre-sized organic host frameworks. Nature 378, 469–471 (1995).

    Article  CAS  Google Scholar 

  6. Mal, P., Breiner, B., Rissanen, K. & Nitschke, J. R. White phosphorus is air-stable within a self-assembled tetrahedral capsule. Science 324, 1697–1699 (2009).

    Article  CAS  PubMed  Google Scholar 

  7. Zhang, D., Ronson, T. K., Zou, Y.-Q. & Nitschke, J. R. Metal–organic cages for molecular separations. Nat. Rev. Chem. 5, 168–182 (2021).

    Article  CAS  PubMed  Google Scholar 

  8. Galan, A. & Ballester, P. Stabilization of reactive species by supramolecular encapsulation. Chem. Soc. Rev. 45, 1720–1737 (2016).

    Article  CAS  PubMed  Google Scholar 

  9. Brown, C. J., Toste, F. D., Bergman, R. G. & Raymond, K. N. Supramolecular catalysis in metal–ligand cluster hosts. Chem. Rev. 115, 3012–3035 (2015).

    Article  CAS  PubMed  Google Scholar 

  10. Chen, L.-J., Yang, H.-B. & Shionoya, M. Chiral metallosupramolecular architectures. Chem. Soc. Rev. 46, 2555–2576 (2017).

    Article  CAS  PubMed  Google Scholar 

  11. Brzechwa-Chodzyńska, A., Drożdż, W., Harrowfield, J. & Stefankiewicz, A. R. Fluorescent sensors: a bright future for cages. Coord. Chem. Rev. 434, 213820 (2021).

    Article  Google Scholar 

  12. Goeb, S. & Sallé, M. Electron-rich coordination receptors based on tetrathiafulvalene derivatives: controlling the host–guest binding. Acc. Chem. Res. 54, 1043–1055 (2021).

    Article  CAS  PubMed  Google Scholar 

  13. Wu, K. et al. The redox coupling effect in a photocatalytic RuII-PdII cage with TTF guest as electron relay mediator for visible-light hydrogen-evolving promotion. Angew. Chem. Int. Ed. 59, 2639–2643 (2020).

    Article  CAS  Google Scholar 

  14. Wezenberg, S. J. Light-switchable metal-organic cages. Chem. Lett. 49, 609–615 (2020).

    Article  CAS  Google Scholar 

  15. Li, R.-J., Tessarolo, J., Lee, H. & Clever, G. H. Multi-stimuli control over assembly and guest binding in metallo-supramolecular hosts based on dithienylethene photoswitches. J. Am. Chem. Soc. 143, 3865–3873 (2021).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  16. Chakrabarty, R., Mukherjee, P. S. & Stang, P. J. Supramolecular coordination: self-assembly of finite two- and three-dimensional ensembles. Chem. Rev. 111, 6810–6918 (2011).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  17. Fujita, D. et al. Self-assembly of tetravalent Goldberg polyhedra from 144 small components. Nature 540, 563–566 (2016).

    Article  CAS  PubMed  Google Scholar 

  18. Wu, K., Tessarolo, J., Baksi, A. & Clever, G. H. Guest-modulated circularly polarized luminescence by ligand-to-ligand chirality transfer in heteroleptic Pdii coordination cages. Angew. Chem. Int. Ed. 61, e202205725 (2022).

    Article  CAS  Google Scholar 

  19. Frank, M. et al. Light-induced charge separation in densely packed donor–acceptor coordination cages. J. Am. Chem. Soc. 138, 8279–8287 (2016).

    Article  CAS  PubMed  Google Scholar 

  20. García-Simón, C. et al. Enantioselective hydroformylation by a Rh-catalyst entrapped in a supramolecular metallocage. J. Am. Chem. Soc. 137, 2680–2687 (2015).

    Article  PubMed  Google Scholar 

  21. Wang, Q.-Q. et al. Self-assembled nanospheres with multiple endohedral binding sites pre-organize catalysts and substrates for highly efficient reactions. Nat. Chem. 8, 225–230 (2016).

    Article  CAS  PubMed  Google Scholar 

  22. Howlader, P., Das, P., Zangrando, E. & Mukherjee, P. S. Urea-functionalized self-assembled molecular prism for heterogeneous catalysis in water. J. Am. Chem. Soc. 138, 1668–1676 (2016).

    Article  CAS  PubMed  Google Scholar 

  23. Pruchyathamkorn, J. et al. A complex comprising a cyanine dye rotaxane and a porphyrin nanoring as a model light-harvesting system. Angew. Chem. Int. Ed. 59, 16455–16458 (2020).

    Article  CAS  Google Scholar 

  24. Wang, W. et al. The construction of complex multicomponent supramolecular systems via the combination of orthogonal self-assembly and the self-sorting approach. Chem. Sci. 5, 4554–4560 (2014).

    Article  CAS  Google Scholar 

  25. Kramer, R., Lehn, J. M. & Marquis-Rigault, A. Self-recognition in helicate self-assembly: spontaneous formation of helical metal complexes from mixtures of ligands and metal ions. Proc. Natl Acad. Sci. USA 90, 5394–5398 (1993).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  26. Sauvage, J. P. & Weiss, J. Synthesis of biscopper(I) [3]-catenates: multiring interlocked coordinating systems. J. Am. Chem. Soc. 107, 6108–6110 (1985).

    Article  CAS  PubMed  Google Scholar 

  27. Kumazawa, K., Biradha, K., Kusukawa, T., Okano, T. & Fujita, M. Multicomponent assembly of a pyrazine-pillared coordination cage that selectively binds planar guests by intercalation. Angew. Chem. Int. Ed. 42, 3909–3913 (2003).

    Article  CAS  Google Scholar 

  28. Zheng, Y.-R. et al. A facile approach toward multicomponent supramolecular structures: selective self-assembly via charge separation. J. Am. Chem. Soc. 132, 16873–16882 (2010).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  29. Wessjohann, L. A., Kreye, O. & Rivera, D. G. One-pot assembly of amino acid bridged hybrid macromulticyclic cages through multiple multicomponent macrocyclizations. Angew. Chem. Int. Ed. 56, 3501–3505 (2017).

    Article  CAS  Google Scholar 

  30. He, Z., Jiang, W. & Schalley, C. A. Integrative self-sorting: a versatile strategy for the construction of complex supramolecular architecture. Chem. Soc. Rev. 44, 779–789 (2015).

    Article  CAS  PubMed  Google Scholar 

  31. Pullen, S., Tessarolo, J. & Clever, G. H. Increasing structural and functional complexity in self-assembled coordination cages. Chem. Sci. 12, 7269–7293 (2021).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  32. Sun, Q.-F., Sato, S. & Fujita, M. An M12(L1)12(L2)12 cantellated tetrahedron: a case study on mixed-ligand self-assembly. Angew. Chem. Int. Ed. 53, 13510–13513 (2014).

    Article  CAS  Google Scholar 

  33. Bloch, W. M. et al. Geometric complementarity in assembly and guest recognition of a bent heteroleptic cis-[Pd2LA2LB2] coordination cage. J. Am. Chem. Soc. 138, 13750–13755 (2016).

    Article  CAS  PubMed  Google Scholar 

  34. Sudan, S. et al. Identification of a heteroleptic Pd6L6L′6 coordination cage by screening of a virtual combinatorial library. J. Am. Chem. Soc. 143, 1773–1778 (2021).

    Article  CAS  PubMed  Google Scholar 

  35. Li, J.-R. & Zhou, H.-C. Bridging-ligand-substitution strategy for the preparation of metal-organic polyhedra. Nat. Chem. 2, 893–898 (2010).

  36. Prusty, S., Yazaki, K., Yoshizawa, M. & Chand, D. K. A truncated molecular star. Chem. Eur. J. 23, 12456–12461 (2017).

    Article  CAS  PubMed  Google Scholar 

  37. Yamashina, M., Yuki, T., Sei, Y., Akita, M. & Yoshizawa, M. Anisotropic expansion of an M2L4 coordination capsule: host capability and frame rearrangement. Chem. Eur. J. 21, 4200–4204 (2015).

    Article  CAS  PubMed  Google Scholar 

  38. Chen, B., Holstein, J. J., Horiuchi, S., Hiller, W. G. & Clever, G. H. Pd(II) coordination sphere engineering: pyridine cages, quinoline bowls, and heteroleptic pills binding one or two fullerenes. J. Am. Chem. Soc. 141, 8907–8913 (2019).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  39. Preston, D., Barnsley, J. E., Gordon, K. C. & Crowley, J. D. Controlled formation of heteroleptic [Pd2(La)2(Lb)2]4+ cages. J. Am. Chem. Soc. 138, 10578–10585 (2016).

    Article  CAS  PubMed  Google Scholar 

  40. Ogata, D. & Yuasa, J. Dynamic open coordination cage from nonsymmetrical imidazole–pyridine ditopic ligands for turn-on/off anion binding. Angew. Chem. Int. Ed. 58, 18424–18428 (2019).

    Article  CAS  Google Scholar 

  41. Lewis, J. E. M., Tarzia, A., White, A. J. P. & Jelfs, K. E. Conformational control of Pd2L4 assemblies with unsymmetrical ligands. Chem. Sci. 11, 677–683 (2020).

    Article  CAS  Google Scholar 

  42. Tessarolo, J., Lee, H., Sakuda, E., Umakoshi, K. & Clever, G. H. Integrative assembly of heteroleptic tetrahedra controlled by backbone steric bulk. J. Am. Chem. Soc. 143, 6339–6344 (2021).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  43. De, S., Mahata, K. & Schmittel, M. Metal-coordination-driven dynamic heteroleptic architectures. Chem. Soc. Rev. 39, 1555–1575 (2010).

    Article  CAS  PubMed  Google Scholar 

  44. Johnson, A. M. & Hooley, R. J. Steric effects control self-sorting in self-assembled clusters. Inorg. Chem. 50, 4671–4673 (2011).

    Article  CAS  PubMed  Google Scholar 

  45. Liu, Y. et al. Controlled construction of heteroleptic [Pd2(LA)2(LB)(LC)]4+ cages: a facile approach for site-selective endo-functionalization of supramolecular cavities. Angew. Chem. Int. Ed. 62, e202217215 (2023).

    Article  CAS  Google Scholar 

  46. Abe, T., Sanada. N., Takeuchi, K., Okazawa, A. & Hiraoka, S. Assembly of six types of heteroleptic Pd2L4 cages under kinetic control, J. Am. Chem. Soc. 146, (2024), https://doi.org/10.1021/jacs.3c09359

  47. Wu, K., Zhang, B., Drechsler, C., Holstein, J. J. & Clever, G. H. Backbone-bridging promotes diversity in heteroleptic cages. Angew. Chem. Int. Ed. 60, 6403–6407 (2021).

    Article  CAS  Google Scholar 

  48. Ebbert, K. E. et al. Resolution of minor size differences in a family of heteroleptic coordination cages by trapped ion mobility ESI-MS. Dalton Trans. 48, 11070–11075 (2019).

    Article  CAS  PubMed  Google Scholar 

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Acknowledgements

We thank the European Research Council (ERC Consolidator Grant 683083, RAMSES) for financial support. This work was funded by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) under Germany’s Excellence Strategy EXC 2033 ‘RESOLV’, project number 390677874, and GRK2376 ‘Confinement‐Controlled Chemistry’, project number 331085229. We thank B. Chen, J. Tessarolo, A. Platzek, K. Ebbert and S. Hasegawa for providing ligands and L. Schneider for ESI mass spectra measurements. We thank J. J. Holstein for helpful suggestions on the crystallographic data analysis.

Author information

Author notes

  1. Ananya Baksi

    Present address: Department of Chemistry, Jadavpur University, Kolkata, India

Authors and Affiliations

  1. Department of Chemistry and Chemical Biology, TU Dortmund University, Dortmund, Germany

    Kai Wu, Elie Benchimol, Ananya Baksi & Guido H. Clever

  2. MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, LIFM, IGCME, School of Chemistry, Sun Yat-Sen University, Guangzhou, China

    Kai Wu

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Contributions

K.W. and G.H.C. conceived the project and wrote the manuscript together with E.B.; K.W. performed the experiments and analysed the data. A.B. provided ion mobility mass measurements. K.W. collected the X-ray single-crystal data and refined the crystal structures.

Corresponding author

Correspondence to Guido H. Clever.

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The authors declare no competing interests.

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Peer review information

Nature Chemistry thanks Xiaopeng Li and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–308 and Tables 1–9.

Supplementary Data 1

Crystallographic data for trans-[Pd2A2B2](BF4)4 (CCDC reference 2207621).

Supplementary Data 2

Crystallographic data for [Pd2B2CD1](BF4)4 (CCDC reference 2285849).

Supplementary Data 3

Crystallographic data for [Pd2A2CD](BF4)4 (CCDC reference 2207623).

Supplementary Data 4

Crystallographic data for [Pd2B2D4C](BF4)4 (CCDC reference 2285847).

Supplementary Data 5

Crystallographic data for [Pd2ABCD](BF4)4 (CCDC reference 2285846).

Supplementary Data 6

Crystallographic data for [Pd2AB0CD](BF4)4 (CCDC reference 2207626).

Supplementary Data 7

Crystallographic data for [Pd2ABD4C](BF4)4 (CCDC reference 2207627).

Supplementary Data 8

Crystallographic data for [Pd2ABD2D](BF4)4 (CCDC reference 2207628).

Supplementary Data 9

Crystallographic data for [Pd2ABCD2](BF4)4 (CCDC reference 2285848).

Source data

Source Data Fig. 2

HR-ESI-MS of cage [Pd2ABCD]4+.

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Wu, K., Benchimol, E., Baksi, A. et al. Non-statistical assembly of multicomponent [Pd2ABCD] cages. Nat. Chem. 16, 584–591 (2024). https://doi.org/10.1038/s41557-023-01415-7

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