The role of carboxylate ligand orbitals in the breathing dynamics of a metal-organic framework by resonant X-ray emission spectroscopy
open access.
| Veröffentlicht in: | Journal of synchrotron radiation. - 1994. - 31(2024), Pt 2 vom: 01. März, Seite 217-221 |
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| 1. Verfasser: | |
| Weitere Verfasser: | , , , , , |
| Format: | Online-Aufsatz |
| Sprache: | English |
| Veröffentlicht: |
2024
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| Zugriff auf das übergeordnete Werk: | Journal of synchrotron radiation |
| Schlagworte: | Journal Article metal-organic framework phase transition resonant X-ray emission spectroscopy |
| Zusammenfassung: | open access. Metal-organic frameworks (MOFs) exhibit structural flexibility induced by temperature and guest adsorption, as demonstrated in the structural breathing transition in certain MOFs between narrow-pore and large-pore phases. Soft modes were suggested to entropically drive such pore breathing through enhanced vibrational dynamics at high temperatures. In this work, oxygen K-edge resonant X-ray emission spectroscopy of the MIL-53(Al) MOF was performed to selectively probe the electronic perturbation accompanying pore breathing dynamics at the ligand carboxylate site for metal-ligand interaction. It was observed that the temperature-induced vibrational dynamics involves switching occupancy between antisymmetric and symmetric configurations of the carboxylate oxygen lone pair orbitals, through which electron density around carboxylate oxygen sites is redistributed and metal-ligand interactions are tuned. In turn, water adsorption involves an additional perturbation of π orbitals not observed in the structural change solely induced by temperature |
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| Beschreibung: | Date Revised 07.03.2024 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
| ISSN: | 1600-5775 |
| DOI: | 10.1107/S1600577524000584 |