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Reversible transformations between the non-porous phases of a flexible coordination network enabled by transient porosity
Date
2023
Abstract
Flexible metal–organic materials that exhibit stimulus-responsive switching between closed (non-porous) and open (porous) structures induced by gas molecules are of potential utility in gas storage and separation. Such behaviour is currently limited to a few dozen physisorbents that typically switch through a breathing mechanism requiring structural contortions. Here we show a clathrate (non-porous) coordination network that undergoes gas-induced switching between multiple non-porous phases through transient porosity, which involves the diffusion of guests between discrete voids through intra-network distortions. This material is synthesized as a clathrate phase with solvent-filled cavities; evacuation affords a single-crystal to single-crystal transformation to a phase with smaller cavities. At 298 K, carbon dioxide, acetylene, ethylene and ethane induce reversible switching between guest-free and gas-loaded clathrate phases. For carbon dioxide and acetylene at cryogenic temperatures, phases showing progressively higher loadings were observed and characterized using in situ X-ray diffraction, and the mechanism of diffusion was computationally elucidated.
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Description
Publisher
Springer
Citation
Nature Chemisstry, 2023, 15, pp. 542–549
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Funding Information
We gratefully acknowledge support from the Irish Research Council (IRCLA/2019/167). We also thank the National Research Foundation of South Africa for financial support. Additionally, we appreciate financial support from KAKENHI Grants-in-Aid for Scientific Research (S) (JP22H05005) and Scientific Research (C) (JP22K05128) from the Japan Society for the Promotion of Science. K.A.F., C.J.S-S. and B.S. also acknowledge support from the Hydrogen and Fuel Cell Technologies Ofice and Vehicle Technologies Ofice within the US Department of Energy’s Ofice of Energy Eficiency and Renewable Energy (award DE-EE0008812). Computational resources were made available by an XSEDE grant (TG-DMR090028), as well as high-performance computing services at North Carolina State University.