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Adaptive response of a metal–organic framework through reversible disorder–disorder transitions

Abstract

The ultrahigh porosity and varied functionalities of porous metal–organic frameworks make them excellent candidates for applications that range widely from gas storage and separation to catalysis and sensing. An interesting feature of some frameworks is the ability to open their pores to a specific guest, enabling highly selective separation. A prerequisite for this is bistability of the host structure, which enables the framework to breathe, that is, to switch between two stability minima in response to its environment. Here we describe a porous framework DUT-8(Ni)—which consists of nickel paddle wheel clusters and carboxylate linkers—that adopts a configurationally degenerate family of disordered states in the presence of specific guests. This disorder originates from the nonlinear linkers arranging the clusters in closed loops of different local symmetries that in turn propagate as complex tilings. Solvent exchange stimulates the formation of distinct disordered frameworks, as demonstrated by high-resolution transmission electron microscopy and diffraction techniques. Guest exchange was shown to stimulate repeatable switching transitions between distinct disorder states.

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Fig. 1: Structure of DUT-8 and anomalous diffraction behaviour.
Fig. 2: Models of disorder in DUT-8.
Fig. 3: Experimental realization of disordered DUT-8 states.
Fig. 4: Electron microscopy analysis of disordered DUT-8(Ni) nanocrystals.
Fig. 5: Characterization by NMR spectroscopy.

Data availability

The data supporting the findings of this study are available within the article and its Supplementary Information. The corresponding raw data are available from the corresponding authors. Crystallographic data for the single-crystal structures can be obtained free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif, under the deposition nos. CCDC-1989709 (DMF@DUT-8(Ni), polymorph A); CCDC-1989708 (DMF@DUT-8(Ni), polymorph B); CCDC-1989557 (NMP@DUT-8(Ni), single domain); CCDC-1989558 (NMP@DUT-8(Ni), four-component twin); CCDC-1989559 (toluene@DUT-8(Ni), single domain) and CCDC-1989560 (toluene@DUT-8(Ni), four-component twin). For each solvent, further details about the two independent refinements considering a single domain crystal and a four-component twin are explained in the Methods and Supplementary Information.

Code availability

All custom code used for the disorder analysis in this study was developed using widely available algorithms. Copies of the actual code used can be obtained on request from A.L.G. Computational data supporting the findings in Supplementary Section 10 are available from the public GitHub online repository at https://github.com/jackevansadl/supp-data.

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Acknowledgements

We thank the German Science Foundation (DFG) (FOR2433) for financial support. We thank HZB for allocation of the synchrotron radiation beamtime and financial support. V.B. thanks the BMBF (project no. 05K19OD2) for financial support. T.E.G. is grateful to DFG for financial support (project CRC 1279). J.D.E. acknowledges the support of the Alexander von Humboldt foundation and HPC platforms provided by the Center for Information Services and High-Performance Computing (ZIH) at TU Dresden. A.L.G. gratefully acknowledges the European Research Council for financial support (advanced grant no. 788144). This project received funding from the European Union (EU) Horizon 2020 Research and an Innovation Programme under Marie Sklodowska-Curie grant agreement no. 641887 (project acronym DEFNET).

Author information

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Authors

Contributions

S.E. and V.B. synthesized and characterized all materials by X-ray diffraction. M.S.W. supported the collection of single crystal X-ray data. E.R. and A.L.G. developed the disorder models. I.S., T.E.G. and U.K. analysed the domain structure of nanocrystals using TEM and electron diffraction data. J.D.E. performed molecular simulations. M.R. and E.B. performed and interpreted the 2H NMR spectra. M.M. and A.P. measured and interpreted the EPR spectra. A.L.G. and S.K. initiated and scientifically guided the study. All authors contributed to writing and improving the manuscript.

Corresponding authors

Correspondence to A. L. Goodwin or S. Kaskel.

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The authors declare no competing interests.

Additional information

Peer review information Nature Chemistry thanks Richard Catlow, João Rocha, Christian Serre and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Extended data

Extended Data Fig. 1 Illustration of the tile symbols.

a, Representation of type 1 (C2h) and type 2 (D2d) loops satisfying the registry requirement for closed loops by arrows indicating up and down steps of the 2,6-ndc linker. b, Transformation of the 6 loops into colour-coded tiles. c, Representative transformation scheme of one loop from arrow scheme to a tile with tongue and groove.

Extended Data Fig. 2 Tiling of the two ordered polymorphs.

Polymorphs A and B represent only two limiting, ordered instances made of pure D2d or C2h tilings, respectively, within a much larger configurational landscape.

Extended Data Fig. 3 Illustration of disorder variants and the corresponding local paddle wheel symmetry.

a, Variation of the probability ϕ for a 5x5 superstructure in 3 representative disorder configurations only containing type 1 (C2h) loops. b, Representation of local paddle wheel variants.

Extended Data Fig. 4 Illustration of the formation of microdomains.

Representative 16x16 superstructure containing C2h and D2d loops.

Extended Data Fig. 5 Entire configurational space of potential and experimentally observed disorder variants.

a, Localization of disorder configurations in ϕ−η space. Each coloured tiling illustrates a guest-specific characteristic disordered state. b, Lateral view of a representative disorder configuration.

Extended Data Fig. 6 Single crystal X-ray observations for ‘as made’ DUT-8(Ni).

Representation of (hk0), (hk1), (hk2) and (hk3) reciprocal lattice planes of DMF@DUT-8(Ni), indicating the presence of both monoclinic (type 1, C2h) and tetragonal (type 2, D2d) domains in the structure.

Extended Data Fig. 7 Single crystal X-ray observations for solvent exchanged DUT-8(Ni).

a, Representation of (hk0), (hk1) and (hk2) reciprocal planes for NMP@DUT-8(Ni). b, Reciprocal planes of toluene@DUT-8(Ni).

Extended Data Fig. 8 Electron diffraction data.

a, Kinematically simulated electron diffraction patterns of tetragonal phase of DUT-8(Ni) along [110] zone. b, Simulated EDF patterns along [331] zone. c, Experimental electron diffraction pattern of as made DUT-8(Ni).

Extended Data Fig. 9 Simulated NMR spectra.

The shape of 2H NMR spectra was modelled for various scenarios differing in linker dynamics.

Supplementary information

Supplementary Information

Supplementary Figs. 1–17, Sections 1–10 and Tables 1–9.

Supplementary Data 1

CCDC-1989709 contains the supplementary crystallographic data for DMF solvated DUT-8(Ni) refined as polymorph A.

Supplementary Data 2

CCDC-1989708 contains the supplementary crystallographic data for DMF solvated DUT-8(Ni) refined as polymorph B.

Supplementary Data 3

CCDC-1989557 contains the supplementary crystallographic data for NMP solvated DUT-8(Ni) refined as a single-domain crystal.

Supplementary Data 4

CCDC-1989558 contains the supplementary crystallographic data for NMP solvated DUT-8(Ni) refined as a four-component twin.

Supplementary Data 5

CCDC-1989559 contains the supplementary crystallographic data for toluene solvated DUT-8(Ni) refined as a single domain crystal.

Supplementary Data 6

CCDC-1989560 contains the supplementary crystallographic data for toluene solvated DUT-8(Ni) refined as a four-component twin.

Supplementary Data 7

Source data for the Supplementary Figs. 15 and 17.

Supplementary Data 8

Results from [CREST] (https://xtb-docs.readthedocs.io/en/latest/crestversions.html) analysis of the PW cluster present in the DUT-8 framework and interactions with solvent molecules. -[mono_dcm](mono_dcm): Monolinic symmetry with DCM molecules. -[mono_dmf](mono_dmf): Monolinic symmetry with DMF molecules. -[tetra_dcm](tetra_dcm): tetragonal symmetry with DCM molecules. -[tetra_dmf](tetra_dmf): tetragonal symmetry with DMF molecules.

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Ehrling, S., Reynolds, E.M., Bon, V. et al. Adaptive response of a metal–organic framework through reversible disorder–disorder transitions. Nat. Chem. 13, 568–574 (2021). https://doi.org/10.1038/s41557-021-00684-4

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