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.
Nikolayenko, Varvara I., et al. "Reversible transformations between the non-porous phases of a flexible coordination network enabled by transient porosity." Nature Chemistry, vol. 15, no. 4, Feb. 2023. https://doi.org/10.1038/s41557-022-01128-3
Nikolayenko, Varvara I., Castell, Dominic C., Sensharma, Debobroto, Shivanna, Mohana, Loots, Leigh, Forrest, Katherine A., Solanilla-Salinas, Carlos J., Otake, Ken-ichi, Kitagawa, Susumu, Barbour, Leonard J., Space, Brian, & Zaworotko, Michael J. (2023). Reversible transformations between the non-porous phases of a flexible coordination network enabled by transient porosity. Nature Chemistry, 15(4). https://doi.org/10.1038/s41557-022-01128-3
Nikolayenko, Varvara I., Castell, Dominic C., Sensharma, Debobroto, et al., "Reversible transformations between the non-porous phases of a flexible coordination network enabled by transient porosity," Nature Chemistry 15, no. 4 (2023), https://doi.org/10.1038/s41557-022-01128-3
@article{osti_2418688,
author = {Nikolayenko, Varvara I. and Castell, Dominic C. and Sensharma, Debobroto and Shivanna, Mohana and Loots, Leigh and Forrest, Katherine A. and Solanilla-Salinas, Carlos J. and Otake, Ken-ichi and Kitagawa, Susumu and Barbour, Leonard J. and others},
title = {Reversible transformations between the non-porous phases of a flexible coordination network enabled by transient porosity},
annote = {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.},
doi = {10.1038/s41557-022-01128-3},
url = {https://www.osti.gov/biblio/2418688},
journal = {Nature Chemistry},
issn = {ISSN 1755-4330},
number = {4},
volume = {15},
place = {United States},
publisher = {Nature Publishing Group},
year = {2023},
month = {02}}