Flux-mediated ligand exchange restructures metal–organic framework glasses
8 affiliations
- 1Department of Chemistry and Chemical Biology, TU Dortmund University, Dortmund, Germany
- 2Inorganic Chemistry and Center for Sustainable Systems Design (CSSD), Faculty of Science, Paderborn University, Paderborn, Germany
- 3Multifunctional Materials & Composites (MMC) Laboratory, Department of Engineering Science, University of Oxford, Oxford, UK
- 4TriboDynamics Lab, Department of Mechanics, Mathematics and Management, Politecnico di Bari, Bari, Italy
- 5Faculty of Physics and Center for Nanointegration Duisburg-Essen (CENIDE), University of Duisburg-Essen, Duisburg, Germany
- 6Department of Chemistry, SRM University-AP, Amaravati, India
- 7Department of Chemistry and Chemical Biology, TU Dortmund University, Dortmund, Germany. [email protected]
- 8Dortmund Center for Advanced Exploration of Dynamics Across Limits Using Spectroscopy (DAEDALUS), TU Dortmund University, Dortmund, Germany. [email protected]
Abstract
Melt-quenched glasses derived from metal–organic frameworks (MOFs) combine the processability of glasses with the modularity and microporosity of MOFs, yet remain structurally and functionally less diverse than crystalline analogues. Here we show that the chelating ligand 1,10-phenanthroline acts as an organic flux that lowers the glass transition temperature of selected MOFs and induces ligand exchange during melting, thereby enabling control over local coordination and global topology in MOF glasses. In Co 2+ -based systems, phenanthroline coordinates to the metal nodes, increases the coordination number and reduces network connectivity by forming terminal ligands. This coordination sphere engineering affords a level of structural control not readily achievable in conventional inorganic or organic glasses. Crucially, the lower processing temperature suppresses thermal decomposition, enabling the synthesis of Co 2+ -based MOF glasses free of magnetic impurities. These glasses exhibit antiferromagnetic coupling and represent unique examples of magnetic MOF glasses formed by melt quenching. Finally, we extend the strategy to otherwise non-meltable carboxylate-based MOFs, establishing flux-mediated ligand exchange as a versatile route to hybrid glasses with tailored connectivity and properties.
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BibTeX
@article{weiß2026fluxmediated,
title = {{Flux-mediated ligand exchange restructures metal–organic framework glasses}},
author = {Jan‐Benedikt Weiß and Lorena Fritsch and Michele Tricarico and Anke Schoch and Soma Salamon and Wen‐Long Xue and Chinmoy Das and Pascal Kolodzeiski and Heiko Wende and Jin‐Chong Tan and Matthias Bauer and Sebastian Henke},
journal = {Nature Materials},
year = {2026},
month = aug,
doi = {10.1038/s41563-026-02712-5},
url = {https://doi.org/10.1038/s41563-026-02712-5},
note = {CC BY},
}
RIS
TY - JOUR
TI - Flux-mediated ligand exchange restructures metal–organic framework glasses
AU - Jan‐Benedikt Weiß
AU - Lorena Fritsch
AU - Michele Tricarico
AU - Anke Schoch
AU - Soma Salamon
AU - Wen‐Long Xue
AU - Chinmoy Das
AU - Pascal Kolodzeiski
AU - Heiko Wende
AU - Jin‐Chong Tan
AU - Matthias Bauer
AU - Sebastian Henke
PY - 2026
DA - 2026/08/24
JO - Nature Materials
DO - 10.1038/s41563-026-02712-5
UR - https://doi.org/10.1038/s41563-026-02712-5
AB - Melt-quenched glasses derived from metal–organic frameworks (MOFs) combine the processability of glasses with the modularity and microporosity of MOFs, yet remain structurally and functionally less diverse than crystalline analogues. Here we show that the chelating ligand 1,10-phenanthroline acts as an organic flux that lowers the glass transition temperature of selected MOFs and induces ligand exchange during melting, thereby enabling control over local coordination and global topology in MOF glasses. In Co 2+ -based systems, phenanthroline coordinates to the metal nodes, increases the coordination number and reduces network connectivity by forming terminal ligands. This coordination sphere engineering affords a level of structural control not readily achievable in conventional inorganic or organic glasses. Crucially, the lower processing temperature suppresses thermal decomposition, enabling the synthesis of Co 2+ -based MOF glasses free of magnetic impurities. These glasses exhibit antiferromagnetic coupling and represent unique examples of magnetic MOF glasses formed by melt quenching. Finally, we extend the strategy to otherwise non-meltable carboxylate-based MOFs, establishing flux-mediated ligand exchange as a versatile route to hybrid glasses with tailored connectivity and properties.
SN - 1476-1122
SN - 1476-4660
ER -