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Reversible transformations between the non-porous phases of a flexible coordination network enabled by transient porosity

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posted on 2023-08-10, 14:33 authored by Varvara Igorivna NikolayenkoVarvara Igorivna Nikolayenko, Dominic CastellDominic Castell, DEBOBROTO SENSHARMADEBOBROTO SENSHARMA, Mohana Shivanna, Leigh Loots, Katherine A. Forrest, Carlos J. Solanilla-Salinas, Ken‐ichi Otake, Susumu Kitagawa, Leonard J. Barbour, Brian Space, MICHAEL ZAWOROTKOMICHAEL ZAWOROTKO

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 difusion of guests between discrete voids through intra-network distortions. This material is synthesized as a clathrate phase with solvent-flled cavities; evacuation afords 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 difraction, and the mechanism of diffusion was computationally elucidated.


SYNergistic SORBents

European Research Council

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Crystal Engineering of Task-Specific Materials

Science Foundation Ireland

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Green Adsorbents for Clean Energy (GrACE)

Science Foundation Ireland

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Nature Chemisstry, 2023, 15, pp. 542–549



Other 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.

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