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A coordination network that reversibly switches between two nonporous polymorphs and a high surface area porous phase
Date
2018
Abstract
We report a 2-fold interpenetrated primitive cubic (pcu) network X-pcu-5-Zn, [Zn2(DMTDC)2(dpe)] (H2DMTDC = 3,4-dimethylthieno[2,3-b]thiophene-2,5-dicarboxylic acid, dpe = 1,2-di(4-pyridyl)ethylene), that exhibits reversible switching between an as-synthesized â openâ phase, X-pcu-5-Zn-α, and two nonporous or â closedâ polymorphs, X-pcu-5-Zn-β and X-pcu-5-Zn-γ. There are two unusual features of X-pcu-5-Zn. The first relates to its sorption properties, which reveal that the α form exhibits high CO2 uptake (ca. 255 cm3/g at 195 K) via reversible closed-to-open switching (type F-IV isotherm) of the type desirable for gas and vapor storage; there are only three other reports of porous materials that combine these two features. Second, we could only isolate the β form by activation of the CO2 loaded α form and it persists through multiple CO2 adsorption/desorption cycles. We are unaware of a new polymorph having been isolated in such a manner. That the observed phase changes of X-pcu-5-Zn-α occur in single-crystal-to-single-crystal fashion enabled structural characterization of the three forms; γ is a coordination isomer of α and β, both of which are based upon â paddlewheelâ clusters.
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Description
peer-reviewed
Publisher
American Chemical Society
Citation
Journal of the American Chemical Society;140 (46), pp. 15572-15576
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Funding Information
Science Foundation Ireland (SFI), National Natural Science Foundation of China, China Scholarship Council
Sustainable Development Goals
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Type
Article
Rights
https://creativecommons.org/licenses/by-nc-sa/1.0/