Methyl-rotation dynamics in metal-organic frameworks probed with terahertz spectroscopy

In ZIF-8 and its cobalt analogue ZIF-67, the imidazolate methyl-groups, which point directly into the void space, have been shown to freely rotate - even down to cryogenic temperatures. Using a combination of experimental terahertz time-domain spectroscopy, low-frequency Raman spectroscopy, and stat...

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Bibliographic Details
Published in:Chemical communications (Cambridge, England) England), 2018, Vol.54 (45), p.5776-5779
Main Authors: Li, Qi, Zaczek, Adam J, Korter, Timothy M, Zeitler, J Axel, Ruggiero, Michael T
Format: Article
Language:English
Subjects:
Computer simulation
Cryogenic temperature
Metal-organic frameworks
Rotor dynamics
Spectrum analysis
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Summary:In ZIF-8 and its cobalt analogue ZIF-67, the imidazolate methyl-groups, which point directly into the void space, have been shown to freely rotate - even down to cryogenic temperatures. Using a combination of experimental terahertz time-domain spectroscopy, low-frequency Raman spectroscopy, and state-of-the-art ab initio simulations, the methyl-rotor dynamics in ZIF-8 and ZIF-67 are fully characterized within the context of a quantum-mechanical hindered-rotor model. The results lend insight into the fundamental origins of the experimentally observed methyl-rotor dynamics, and provide valuable insight into the nature of the weak interactions present within this important class of materials.
ISSN:1359-7345
1364-548X
DOI:10.1039/c8cc02650e