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Hetero-interpenetrated metal–organic frameworks

Nature Chemistry volume 15, pages 1358–1364 (2023)Cite this article

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Abstract

Interpenetrated metal–organic frameworks (MOFs) comprise two or more lattices that are mutually entangled. Interpenetration can be used to tune the structures and pore architectures of MOFs to influence, for example, their stability or interactions with guest molecules. The interpenetrating sublattices are typically identical, but hetero-interpenetrated MOFs, which consist of sublattices that are different from one another, have also been serendipitously produced. Here we describe a strategy for the deliberate synthesis of hetero-interpenetrated MOFs. We use the cubic α-MUF-9 framework as a host sublattice to template the growth of a second sublattice within its pores. Three different secondary sublattices are grown—two of which are not known as standalone MOFs—leading to three different hetero-interpenetrated MOFs. This strategy may serve to combine different properties into one material. We produce an asymmetric catalysis by allocating separate roles to the interpenetrating sublattices in a hetero-interpenetrated MOF: an achiral secondary amine on one sublattice provides the catalytic activity, while the chiral α-MUF-10 host imparts asymmetry to aldol and Henry reactions.

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Fig. 1: Hetero-interpenetrated versus homo-interpenetrated MOFs.
Fig. 2: The structures of α-MUF-9 and MUF-91–MUF-93 determined by SCXRD.
Fig. 3: The variation in PIP across an individual crystal of MUF-93 as determined from multiple SCXRD datasets.
Fig. 4: The differentiation of cobalt and zinc sites in hetero-interpenetrated MOFs using the anomalous dispersion of X-rays.
Fig. 5: Hetero-interpenetrated MOFs as asymmetric catalysts.

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Data availability

Crystallographic data for the structures reported in this Article have been deposited at the Cambridge Crystallographic Data Centre, under deposition numbers 2144458–2144473 and 2269651 (MUF-91), 2144574–2144588 (MUF-92), 2149445–2149471 and 2269651 (MUF-93) and 2149424–2149437 (rastering files for MUF-93), as detailed in Supplementary Table 1. Copies of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/. All other data are included in the Supplementary Information. Source data are provided with this article and also available on figshare, https://doi.org/10.6084/m9.figshare.22682965.v2 (ref. 28).

Code availability

The Python scripts are available on figshare at https://doi.org/10.6084/m9.figshare.22682965.v2 (ref. 28).

References

  1. Batten, S. R. Topology of interpenetration. CrystEngComm 3, 67–72 (2001).

    Article  Google Scholar 

  2. Batten, S. R. & Robson, R. Interpenetrating nets: ordered, periodic entanglement. Angew. Chem. Int. Ed. 37, 1460–1494 (1998).

    Article  Google Scholar 

  3. Haldar, R., Sikdar, N. & Maji, T. K. Interpenetration in coordination polymers: structural diversities toward porous functional materials. Mater. Today 18, 97–116 (2015).

    Article  CAS  Google Scholar 

  4. Jiang, H.-L., Makal, T. A. & Zhou, H.-C. Interpenetration control in metal-organic frameworks for functional applications. Coord. Chem. Rev. 257, 2232–2249 (2013).

    Article  CAS  Google Scholar 

  5. Park, J. H. et al. Interpenetration control, sorption behavior, and framework flexibility in Zn(II) metal-organic frameworks. Cryst. Growth Des. 14, 699–704 (2014).

    Article  CAS  Google Scholar 

  6. Verma, G., Butikofer, S., Kumar, S. & Ma, S. Regulation of the degree of interpenetration in metal–organic frameworks. Top. Curr. Chem. 378, 4 (2019).

    Article  Google Scholar 

  7. Deshpande, R. K., Minnaar, J. L. & Telfer, S. G. Thermolabile groups in metal–organic frameworks: suppression of network interpenetration, post-synthetic cavity expansion and protection of reactive functional groups. Angew. Chem. Int. Ed. 47, 4598–4602 (2010).

    Article  Google Scholar 

  8. Miller, J. S. Interpenetrating lattices—materials of the future. Adv. Mater. 13, 525–527 (2001).

    Article  CAS  Google Scholar 

  9. Li, S. et al. A 2D metal-organic framework interpenetrated by a 2D supramolecular framework assembled by CH/ π interactions. Inorg. Chem. Commun. 130, 108705 (2021).

    Article  CAS  Google Scholar 

  10. Zhang, M.-D. et al. Chiral 3D/3D hetero-interpenetrating framework with six kinds of helices, 3D polyrotaxane and 2D network via one-pot reaction. CrystEngComm 15, 227–230 (2013).

    Article  CAS  Google Scholar 

  11. Xu, H. et al. An unprecedented 3D/3D hetero-interpenetrated MOF built from two different nodes, chemical composition, and topology of networks. CrystEngComm 14, 5720–5722 (2012).

    Article  CAS  Google Scholar 

  12. Batten, S. R. in Metal-Organic Frameworks: Design and Application (ed MacGillivray, L. R.) Ch. 3 (John Wiley & Sons, 2010).

  13. Kwon, O., Park, S., Zhou, H. C. & Kim, J. Computational prediction of hetero-interpenetration in metal-organic frameworks. Chem. Commun. 53, 1953–1956 (2017).

    Article  CAS  Google Scholar 

  14. Sezginel, K., Feng, T. & Wilmer, C. Discovery of hypothetical hetero-interpenetrated MOFs with arbitrarily dissimilar topologies and unit cell shapes. CrystEngComm 19, 4497–4504 (2017).

    Article  CAS  Google Scholar 

  15. Furukawa, H., Muller, U. & Yaghi, O. M. “Heterogeneity within order” in metal-organic frameworks. Angew. Chem. Int. Ed. 54, 3417–3430 (2015).

    Article  CAS  Google Scholar 

  16. Pang, Q., Tu, B. & Li, Q. Metal-organic frameworks with multicomponents in order. Coord. Chem. Rev. 388, 107–125 (2019).

    Article  CAS  Google Scholar 

  17. Ferguson, A. et al. Controlled partial interpenetration in metal–organic frameworks. Nat. Chem 8, 250–257 (2016).

    Article  CAS  PubMed  Google Scholar 

  18. Verma, G. et al. Partially interpenetrated NbO topology metal–organic framework exhibiting selective gas adsorption. Cryst. Growth Des. 17, 2711–2717 (2017).

    Article  CAS  Google Scholar 

  19. Yang, S. et al. A partially interpenetrated metal–organic framework for selective hysteretic sorption of carbon dioxide. Nat. Mater. 11, 710–716 (2012).

    Article  CAS  PubMed  Google Scholar 

  20. O’Nolan, D. et al. Impact of partial interpenetration in a hybrid ultramicroporous material on C2H2/C2H4 separation performance. Chem. Commun. 54, 3488–3491 (2018).

    Article  Google Scholar 

  21. Pan, L., Ching, N., Huang, X. & Li, J. Reactions and reactivity of Co−bpdc coordination polymers (bpdc = 4,4′-biphenyldicarboxylate). Inorg. Chem. 39, 5333–5340 (2000).

    Article  CAS  PubMed  Google Scholar 

  22. Hausdorf, S., Baitalow, F., Böhle, T., Rafaja, D. & Mertens, F. O. Main-group and transition-element IRMOF homologues. J. Am. Chem. Soc. 132, 10978–10981 (2010).

    Article  CAS  PubMed  Google Scholar 

  23. Brozek, C. K., Cozzolino, A. F., Teat, S. J., Chen, Y.-S. & Dincă, M. Quantification of site-specific cation exchange in metal–organic frameworks using multi-wavelength anomalous X-ray dispersion. Chem. Mater. 25, 2998–3002 (2013).

    Article  CAS  Google Scholar 

  24. Freedman, D. E. et al. Site specific X-ray anomalous dispersion of the geometrically frustrated kagomé‚ magnet, herbertsmithite, ZnCu3(OH)6Cl2. J. Am. Chem. Soc. 132, 16185–16190 (2010).

    Article  CAS  PubMed  Google Scholar 

  25. Helliwell, M. et al. Determination of zinc incorporation in the Zn-substituted gallophosphate ZnULM-5 by multiple wavelength anomalous dispersion techniques. Acta Cryst.B 66, 345–357 (2010).

    Article  CAS  Google Scholar 

  26. Zhou, T.-Y., Auer, B., Lee, S. J. & Telfer, S. G. Catalysts confined in programmed framework pores enable new transformations and tune reaction efficiency and selectivity. J. Am. Chem. Soc. 141, 1577–1582 (2019).

    Article  CAS  PubMed  Google Scholar 

  27. Ishikawa, H. & Shiomi, S. Alkaloid synthesis using chiral secondary amine organocatalysts. Org. Biomol. Chem. 14, 409–424 (2016).

    Article  CAS  PubMed  Google Scholar 

  28. Perl, D. et al. Data for paper ‘Hetero-interpenetrated metal-organic frameworks’. figshare https://doi.org/10.6084/m9.figshare.22682965.v2 (2023).

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Acknowledgements

This research was undertaken in part using the MX2 beamline at the Australian Synchrotron, part of the Australian Nuclear Science and Technology Organisation. We made use of the Australian Cancer Research Foundation detector, partially funded by the New Zealand Group and supported by Massey University. We are grateful to beamline scientists S. Panjikar and J. Price for their expert help. We also thank D. Lun for technical assistance and P. Plieger for guidance on AA spectroscopy. We received no specific funding for this work.

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Authors and Affiliations

  1. MacDiarmid Institute for Advanced Materials and Nanotechnology, School of Natural Sciences, Massey University, Palmerston North, New Zealand

    David Perl, Seok J. Lee, Alan Ferguson, Geoffrey B. Jameson & Shane G. Telfer

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  1. David Perl
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  3. Alan Ferguson
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Contributions

S.G.T. conceived the idea. D.P. developed the concept, conducted experiments, analysed the results and prepared the Supplementary Information. A.F. and S.J.L. conducted experimental work. G.B.J. conceived and advised on the anomalous scattering experiments. S.G.T. and G.B.J. supervised the project. S.G.T. and D.P. wrote the manuscript with contributions from all authors.

Corresponding author

Correspondence to Shane G. Telfer.

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The authors declare no competing interests.

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Peer review information

Nature Chemistry thanks Hai-Long Jiang, Hong-Cai Zhou 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. 1–30, Tables 1–8 and Methods.

Supplementary Data 1

Crystallographic information files (CIFs) for MUF-91 materials, [Zn4O(L1)3] and [Zn4O(bpdc)3]x.

Supplementary Data 2

CIFs for MUF-92 materials, [Zn4O(L1)3] and [Zn4O(bpdc-NH2)3]x.

Supplementary Data 3

CIFs for MUF-93 materials, [Zn4O(L1)3] and [Co4O(bpdc)3]x.

Supplementary Data 4

Rastering CIFs for MUF-93 materials, [Zn4O(L1)3] and [Co4O(bpdc)3]x.

Supplementary Data 5

Crystallographic files for difference datasets using two different wavelengths.

Supplementary Data 6

Source data for Supplementary Figs. 2, 6, 7, 12, 13a, 14, 16, 26, 27, 28 and 30.

Source data

Source Data Fig. 1

Source data for Figs. 1c–e.

Source Data Fig. 3

Source data for Fig. 3.

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Perl, D., Lee, S.J., Ferguson, A. et al. Hetero-interpenetrated metal–organic frameworks. Nat. Chem. 15, 1358–1364 (2023). https://doi.org/10.1038/s41557-023-01277-z

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