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Desolvation of metal complexes to construct metal–organic framework glasses

Nature Synthesis volume 3, pages 214–223 (2024)Cite this article

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Abstract

Structural design is an important challenge in glassy materials, including metal–organic framework (MOF) glasses. The current approaches of thermal and mechanical vitrification are mainly limited to azolate and cyanide-based crystalline MOFs, as other MOF crystals usually decompose before melting or upon milling instead of forming stable glasses. Here we report a method for the preparation of MOF glasses by the ‘desolvation’ of solvated metal–ligand discrete complexes. MOF glasses with 12 different ligands of varying lengths, shapes, side and coordination groups (carboxylate, pyridyl and azolate) are synthesized. Hydrogen-bonded networks of the metal complexes pre-assemble metal–ligand arrays, which in turn guide the formation of glass during desolvation. Molecular-level structural transformation studies reveal the network-forming glass structures. The prepared glasses have structural diversity, with tunable pores (sizes and modifications) and good processability, and wide glass transition temperatures ranging from 120 °C to 280 °C. The synthesized glasses with larger ligands have higher crystallization temperatures, affording grain-boundary-free and transparent monoliths under heating without pressure.

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Fig. 1: Structures of ligands and metal complexes as precursors for MOF glasses.
Fig. 2: Desolvation of 1mc to form 1g.
Fig. 3: Structural transformation during desolvation and crystallization.
Fig. 4: Structural transformation of 11mc during heating.
Fig. 5: Gas-sorption properties.

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Data availability

Data supporting the findings of the study are available in the paper and its Supplementary Information. Source data are provided with this paper. Crystallographic data for the structures reported in this Article have been deposited at the Cambridge Crystallographic Data Centre, under deposition nos. CCDC 2236539 (1mc), 2236540 (1mc(Zn)), 2236541 (1mc(Mn)), 2236542 (1mc(Cd)), 2236543 (2mc), 2236544 (3mc), 2236545 (4mc), 2236546 (5mc), 2236547 (6mc), 2236548 (7mc), 2236549 (8mc), 2236550 (9mc), 2236551 (10mc), 2236552 (11mc), 2236553 (12mc), 2281239 (5c), 2281240 (6c) and 2281241 (11mc-MeOH). Copies of the data can be obtained free of charge at https://www.ccdc.cam.ac.uk/structures/.

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Acknowledgements

The work was supported by the Japan Society of the Promotion of Science (JSPS) for a Grant-in-Aid for Scientific Research (B) (JP18H02032), Challenging Research (Exploratory) (JP19K22200) and Transformative Research Areas (A) ‘Supra-ceramics’ (JP22H05147) from the Ministry of Education, Culture, Sports, Science and Technology, Japan, The Asahi Glass Foundation, and the NSRF via the Program Management Unit for Human Reseources & Institutional Development, Research and Innovation, Thailand (B40G660034). We acknowledge AichiSR BL11S2 (2020D6005) and SPring-8 BL14B2 beamlines for XAFS, the SPring-8 BL02B2 beamline for PXRD (2023A1748) and the AichiSR BL5S2 beamline for PDF (2021D3036).

Author information

Authors and Affiliations

  1. Institute for Integrated Cell-Material Sciences, Institute for Advanced Study, Kyoto University, Yoshida-Honmachi, Sakyo-ku, Kyoto, Japan

    Yong-Sheng Wei & Satoshi Horike

  2. Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto, Japan

    Zeyu Fan & Cheng Luo

  3. Department of Chemistry, Graduate School of Science, Kyoto University, Kitashirakawa-Oiwakecho, Sakyo-ku, Kyoto, Japan

    Satoshi Horike

  4. Department of Materials Science and Engineering, School of Molecular Science and Engineering, Vidyasirimedhi Institute of Science and Technology, Rayong, Thailand

    Satoshi Horike

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  1. Yong-Sheng Wei
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Contributions

S.H. and Y.-S.W. designed the project. Y.-S.W. synthesized the metal complexes and prepared the glassy compounds. Y.-S.W. collected and analysed powder and carried out single-crystal X-ray diffraction, thermogravimetric analysis, differential scanning calorimetry, scanning electron microscopy, infrared spectroscopy, gas adsorption, synchrotron X-ray absorption and total scattering measurements. Z.F. helped with the analysis of synchrotron data. C.L. helped with the synthesis of metal complexes and powder X-ray diffraction measurements. S.H. and Y.-S.W. wrote the paper, and all authors contributed to revising the paper.

Corresponding authors

Correspondence to Yong-Sheng Wei or Satoshi Horike.

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The authors declare no competing interests.

Peer review

Peer review information

Nature Synthesis thanks Lothar Wondraczek and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Primary Handling Editor: Alison Stoddart, in collaboration with the Nature Synthesis team.

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Supplementary Information

Supplementary Information

Supplementary Figs. 1–71, discussion and Tables 1–5.

Supplementary Video1

Monolith formation from 3mc under heating.

Supplementary Video 2

Monolith formation from 3mc(Cd) under heating.

Supplementary Data 1

Crystallographic data for 1mc, CCDC 2236539.

Supplementary Data 2

Crystallographic data for 1mc(Zn), CCDC 2236540.

Supplementary Data 3

Crystallographic data for 1mc(Mn), CCDC 2236541.

Supplementary Data 4

Crystallographic data for 1mc(Cd), CCDC 2236542.

Supplementary Data 5

Crystallographic data for 2mc, CCDC 2236543.

Supplementary Data 6

Crystallographic data for 3mc, CCDC 2236544.

Supplementary Data 7

Crystallographic data for 4mc, CCDC 2236545

Supplementary Data 8

Crystallographic data for 5mc, CCDC 2236546.

Supplementary Data 9

Crystallographic data for 6mc, CCDC 2236547.

Supplementary Data 10

Crystallographic data for 7mc, CCDC 2236548.

Supplementary Data 11

Crystallographic data for 8mc, CCDC 2236549.

Supplementary Data 12

Crystallographic data for 9mc, CCDC 2236550.

Supplementary Data 13

Crystallographic data for 10mc, CCDC 2236551.

Supplementary Data 14

Crystallographic data for 11mc, CCDC 2236552.

Supplementary Data 15

Crystallographic data for 12mc, CCDC 2236553.

Supplementary Data 16

Crystallographic data for 5c, CCDC 2281239.

Supplementary Data 17

Crystallographic data for 6c, CCDC 2281240.

Supplementary Data 18

Crystallographic data for 11mc-MeOH, CCDC 2281241.

Source data

Source Data Fig. 2

TG-DTA, VT-PXRD, VT-FTIR, PDF data for 1mc under heating; DSC and EXAFS data for 1g.

Source Data Fig. 4

EXAFS data for 11g and VT-FTIR data for 11mc under heating.

Source Data Fig. 5

Gas adsorption data in Fig. 5.

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Wei, YS., Fan, Z., Luo, C. et al. Desolvation of metal complexes to construct metal–organic framework glasses. Nat. Synth 3, 214–223 (2024). https://doi.org/10.1038/s44160-023-00412-5

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