An ultra-dynamic anion-cluster-based organic framework

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Date
2022-01-13
Authors
Samanta, Jayanta
Dorn, Rick W.
Zhang, Wenlin
Jiang, Xuanfeng
Zhang, Mingshi
Staples, Richard J.
Rossini, Aaron J.
Ke, Chenfeng
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Elsevier
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Chemistry
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Ames Laboratory
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ChemistryAmes Laboratory
Abstract
Porous organic frameworks that can dynamically expand their voids to guest uptake remain formidable to design. The challenge comes from finding the balance between rigidity and flexibility. Rigidity is required to retain the framework, and the flexibility is needed for reversible expansion/contraction. Herein, we introduced bisulfate anion clusters as soft joints to construct a single-crystalline hydrogen-bonded cross-linked organic framework HCOF-6. Upon the uptake of guest molecules, the anion clusters of HCOF-6 were disrupted, allowing the crystal to expand rapidly (<40 min) to more than twice its original length. Removing these guests restored the anion clusters and the crystallinity of HCOF-6 quickly (<10 min). These guest-induced material size expansions and contractions are highly reversible, and the dynamic anion cluster dissociation-reassociation is confirmed by molecular dynamics simulations and solid-state NMR experiments. The guest-induced size change of HCOF-6 highlights a new approach to synthesize dynamic framework materials by introducing anion clusters.
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This is a manuscript of an article published as Samanta, Jayanta, Rick W. Dorn, Wenlin Zhang, Xuanfeng Jiang, Mingshi Zhang, Richard J. Staples, Aaron J. Rossini, and Chenfeng Ke. "An ultra-dynamic anion-cluster-based organic framework." Chem 8, no. 1 (2022): 253-267. DOI: 10.1016/j.chempr.2021.11.014. Attribution-NonCommercial-NoDerivatives 4.0 International (CC BY-NC-ND 4.0). Copyright 2021 Elsevier Inc. Posted with permission.
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anion cluster, hydrogen-bonded crosslinked organic framework, crystal expansion and contraction, porous organic framework, crystal engineering, single-crystal-to-single-crystal transformation, hydrogen-bonded organic framework, dynamic framework, elastic crystal
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