Reversible Switching between Nonporous and Porous Phases of a New SIFSIX Coordination Network Induced by a Flexible Linker Ligand

Closed-to-open structural transformations in flexible coordination networks are of potential utility in gas storage and separation. Herein, we report the first example of a flexible SiF -pillared square grid material, [Cu(SiF )(L) ] (L = 1,4-bis(1-imidazolyl)benzene), . exhibits reversible switching...

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Published in:Journal of the American Chemical Society Vol. 142; no. 15; p. 6896
Main Authors: Song, Bai-Qiao, Yang, Qing-Yuan, Wang, Shi-Qiang, Vandichel, Matthias, Kumar, Amrit, Crowley, Clare, Kumar, Naveen, Deng, Cheng-Hua, GasconPerez, Victoria, Lusi, Matteo, Wu, Hui, Zhou, Wei, Zaworotko, Michael J
Format: Journal Article
Language:English
Published: United States 15.04.2020
ISSN:1520-5126, 1520-5126
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Summary:Closed-to-open structural transformations in flexible coordination networks are of potential utility in gas storage and separation. Herein, we report the first example of a flexible SiF -pillared square grid material, [Cu(SiF )(L) ] (L = 1,4-bis(1-imidazolyl)benzene), . exhibits reversible switching between nonporous ( ) and several porous ( , , , and ) phases triggered by exposure to N , CO , or H O. In addition, heating to 433 K resulted in irreversible transformation to a closed polymorph, . Single-crystal X-ray diffraction studies revealed that the phase transformations are enabled by rotation and geometrical contortion of L. Density functional theory calculations indicated that L exhibits a low barrier to rotation (as low as 8 kJmol ) and a rather flat energy surface. In situ neutron powder diffraction studies provided further insight into these sorbate-induced phase changes. combines stability in water for over a year, high CO uptake (ca. 216 cm /g at 195 K), and good thermal stability.
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ISSN:1520-5126
1520-5126
DOI:10.1021/jacs.0c01314