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Dynamics of Linkers in Metal-Organic Framework Glasses.
- Source :
-
Journal of the American Chemical Society [J Am Chem Soc] 2024 May 15; Vol. 146 (19), pp. 12950-12957. Date of Electronic Publication: 2024 May 01. - Publication Year :
- 2024
-
Abstract
- Metal-organic framework (MOF) glasses have emerged as a new class of organic-inorganic hybrid glass materials. Considerable efforts have been devoted to unraveling the macroscopic dynamics of MOF glasses by studying their rheological behavior; however, their microscopic dynamics remain unclear. In this work, we studied the effect of vitrification on linker dynamics in ZIF-62 by solid-state <superscript>2</superscript> H nuclear magnetic resonance (NMR) spectroscopy. <superscript>2</superscript> H NMR relaxation analysis provided a detailed picture of the mobility of the ZIF-62 linkers, including local restricted librations and a large-amplitude twist; these details were verified by molecular dynamics. A comparison of ZIF-62 crystals and glasses revealed that vitrification does not drastically affect the fast individual flipping motions with large-amplitude twists, whereas it facilitates slow cooperative large-amplitude twist motions with a decrease in the activation barrier. These observations support the findings of previous studies, indicating that glassy ZIF-62 retains permanent porosity and that short-range disorder exists in the alignment of ligands because of distortion of the coordination angle.
Details
- Language :
- English
- ISSN :
- 1520-5126
- Volume :
- 146
- Issue :
- 19
- Database :
- MEDLINE
- Journal :
- Journal of the American Chemical Society
- Publication Type :
- Academic Journal
- Accession number :
- 38693778
- Full Text :
- https://doi.org/10.1021/jacs.3c13156