Melt-quenched carboxylate metal–organic framework glasses
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 meta...
| Main Authors: | , , , , , |
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| Format: | Article |
| Language: | English |
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Nature Portfolio
2024-02-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-024-45326-8 |
| _version_ | 1797273915743010816 |
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| author | Minhyuk Kim Hwa-Sub Lee Dong-Hyun Seo Sung June Cho Eun-chae Jeon Hoi Ri Moon |
| author_facet | Minhyuk Kim Hwa-Sub Lee Dong-Hyun Seo Sung June Cho Eun-chae Jeon Hoi Ri Moon |
| author_sort | Minhyuk Kim |
| collection | DOAJ |
| description | 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 (T m) 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 T m may be attributed to the flexibility and low symmetry of the aliphatic carboxylate ligand, which raises the entropy of fusion (ΔS fus), and the lack of crystal field stabilization energy on metal ions, reducing enthalpy of fusion (ΔH fus). This research will serve as a cornerstone for the integration of numerous carboxylate-based MOFs into MOF glasses. |
| first_indexed | 2024-03-07T14:52:01Z |
| format | Article |
| id | doaj.art-d9877039178c44e593e72662cb68207a |
| institution | Directory Open Access Journal |
| issn | 2041-1723 |
| language | English |
| last_indexed | 2024-03-07T14:52:01Z |
| publishDate | 2024-02-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj.art-d9877039178c44e593e72662cb68207a2024-03-05T19:41:44ZengNature PortfolioNature Communications2041-17232024-02-011511910.1038/s41467-024-45326-8Melt-quenched carboxylate metal–organic framework glassesMinhyuk Kim0Hwa-Sub Lee1Dong-Hyun Seo2Sung June Cho3Eun-chae Jeon4Hoi Ri Moon5Department of Chemistry, School of Natural Science, Ulsan National Institute of Science and Technology (UNIST)School of Materials Science and Engineering, University of UlsanMajor of Nano-Mechatronics, University of Science and TechnologyDepartment of Chemical Engineering, Chonnam National UniversitySchool of Materials Science and Engineering, University of UlsanDepartment of Chemistry and Nano Science, Ewha Womans UniversityAbstract 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 (T m) 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 T m may be attributed to the flexibility and low symmetry of the aliphatic carboxylate ligand, which raises the entropy of fusion (ΔS fus), and the lack of crystal field stabilization energy on metal ions, reducing enthalpy of fusion (ΔH fus). This research will serve as a cornerstone for the integration of numerous carboxylate-based MOFs into MOF glasses.https://doi.org/10.1038/s41467-024-45326-8 |
| spellingShingle | Minhyuk Kim Hwa-Sub Lee Dong-Hyun Seo Sung June Cho Eun-chae Jeon Hoi Ri Moon Melt-quenched carboxylate metal–organic framework glasses Nature Communications |
| title | Melt-quenched carboxylate metal–organic framework glasses |
| title_full | Melt-quenched carboxylate metal–organic framework glasses |
| title_fullStr | Melt-quenched carboxylate metal–organic framework glasses |
| title_full_unstemmed | Melt-quenched carboxylate metal–organic framework glasses |
| title_short | Melt-quenched carboxylate metal–organic framework glasses |
| title_sort | melt quenched carboxylate metal organic framework glasses |
| url | https://doi.org/10.1038/s41467-024-45326-8 |
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