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Melt-quenched carboxylate metal–organic framework glasses

Author

Listed:
  • Minhyuk Kim

    (Ulsan National Institute of Science and Technology (UNIST))

  • Hwa-Sub Lee

    (University of Ulsan)

  • Dong-Hyun Seo

    (University of Science and Technology)

  • Sung June Cho

    (Chonnam National University)

  • Eun-chae Jeon

    (University of Ulsan)

  • Hoi Ri Moon

    (Ewha Womans University)

Abstract

Although carboxylate-based frameworks are commonly used architectures in metal-organic frameworks (MOFs), liquid/glass MOFs have thus far mainly been obtained from azole- or weakly coordinating ligand-based frameworks. This is because strong coordination bonds of carboxylate ligands to metals block the thermal vitrification pathways of carboxylate-based MOFs. In this study, we present the example of carboxylate-based melt-quenched MOF glasses comprising Mg2+ or Mn2+ with an aliphatic carboxylate ligand, adipate. These MOFs have a low melting temperature (Tm) of 284 °C and 238 °C, respectively, compared to zeolitic-imidazolate framework (ZIF) glasses, and superior mechanical properties in terms of hardness and elastic modulus. The low Tm may be attributed to the flexibility and low symmetry of the aliphatic carboxylate ligand, which raises the entropy of fusion (ΔSfus), and the lack of crystal field stabilization energy on metal ions, reducing enthalpy of fusion (ΔHfus). This research will serve as a cornerstone for the integration of numerous carboxylate-based MOFs into MOF glasses.

Suggested Citation

  • Minhyuk Kim & Hwa-Sub Lee & Dong-Hyun Seo & Sung June Cho & Eun-chae Jeon & Hoi Ri Moon, 2024. "Melt-quenched carboxylate metal–organic framework glasses," Nature Communications, Nature, vol. 15(1), pages 1-9, December.
    • Handle: RePEc:nat:natcom:v:15:y:2024:i:1:d:10.1038_s41467-024-45326-8
    DOI: 10.1038/s41467-024-45326-8
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    2. Nattapol Ma & Ryo Ohtani & Hung M. Le & Søren S. Sørensen & Ryuta Ishikawa & Satoshi Kawata & Sareeya Bureekaew & Soracha Kosasang & Yoshiyuki Kawazoe & Koji Ohara & Morten M. Smedskjaer & Satoshi Hor, 2022. "Exploration of glassy state in Prussian blue analogues," Nature Communications, Nature, vol. 13(1), pages 1-11, December.
    3. Jingwei Hou & Christopher W. Ashling & Sean M. Collins & Andraž Krajnc & Chao Zhou & Louis Longley & Duncan N. Johnstone & Philip A. Chater & Shichun Li & Marie-Vanessa Coulet & Philip L. Llewellyn & , 2019. "Metal-organic framework crystal-glass composites," Nature Communications, Nature, vol. 10(1), pages 1-10, December.
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