Chris Hawes c.s.hawes@keele.ac.uk
Anisotropic Thermal and Guest-Induced Responses of an Ultramicroporous Framework with Rigid Linkers
Hawes, Chris S.
Authors
Abstract
The interdependent effects of temperature and guest uptake on the structure of the ultramicroporous metal-organic framework [Cu3 (cdm)4 ] (cdm=C(CN)2 (CONH2 )- ) were explored in detail by using in situ neutron scattering and density functional theory calculations. The tetragonal lattice displays an anisotropic thermal response related to a hinged "lattice-fence" mechanism, unusual for this topology, which is facilitated by pivoting of the rigid cdm anion about the Cu nodes. Calculated pore-size metrics clearly illustrate the potential for temperature-mediated adsorption in ultramicroporous frameworks due to thermal fluctuations of the pore diameter near the value of the target guest kinetic diameter, though in [Cu3 (cdm)4 ] this is counteracted by a competing contraction of the pore with increasing temperature as a result of the anisotropic lattice response.
Acceptance Date | Feb 13, 2018 |
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Publication Date | Apr 3, 2018 |
Publicly Available Date | Mar 29, 2024 |
Journal | Chemistry - A European Journal |
Print ISSN | 0947-6539 |
Publisher | Wiley |
Pages | 4774-4779 |
DOI | https://doi.org/10.1002/chem.201800261 |
Keywords | Gas Sorption; negative thermal expansion |
Publisher URL | https://doi.org/10.1002/chem.201800261 |
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