Negative cooperativity upon hydrogen bond-stabilized O2 adsorption in a redox-active metal–organic framework

Julia Oktawiec; Henry Z.H. Jiang; Jenny G. Vitillo; Douglas A. Reed; Lucy E. Darago; Benjamin A. Trump; Varinia Bernales; Harriet Li; Kristen A. Colwell; Hiroyasu Furukawa; Craig M. Brown; Laura Gagliardi; Jeffrey R. Long

doi:10.1038/s41467-020-16897-z

Negative cooperativity upon hydrogen bond-stabilized O₂ adsorption in a redox-active metal–organic framework

Julia Oktawiec, Henry Z.H. Jiang, Jenny G. Vitillo, Douglas A. Reed, Lucy E. Darago, Benjamin A. Trump, Varinia Bernales, Harriet Li, Kristen A. Colwell, Hiroyasu Furukawa, Craig M. Brown, Laura Gagliardi, Jeffrey R. Long

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Abstract

The design of stable adsorbents capable of selectively capturing dioxygen with a high reversible capacity is a crucial goal in functional materials development. Drawing inspiration from biological O₂ carriers, we demonstrate that coupling metal-based electron transfer with secondary coordination sphere effects in the metal–organic framework Co₂(OH)₂(bbta) (H₂bbta = 1H,5H-benzo(1,2-d:4,5-d′)bistriazole) leads to strong and reversible adsorption of O₂. In particular, moderate-strength hydrogen bonding stabilizes a cobalt(III)-superoxo species formed upon O₂ adsorption. Notably, O₂-binding in this material weakens as a function of loading, as a result of negative cooperativity arising from electronic effects within the extended framework lattice. This unprecedented behavior extends the tunable properties that can be used to design metal–organic frameworks for adsorption-based applications.

Original language	English (US)
Article number	3087
Journal	Nature communications
Volume	11
Issue number	1
DOIs	https://doi.org/10.1038/s41467-020-16897-z
State	Published - Dec 1 2020

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Publisher Copyright:
© 2020, The Author(s).

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Oktawiec, J., Jiang, H. Z. H., Vitillo, J. G., Reed, D. A., Darago, L. E., Trump, B. A., Bernales, V., Li, H., Colwell, K. A., Furukawa, H., Brown, C. M., Gagliardi, L., & Long, J. R. (2020). Negative cooperativity upon hydrogen bond-stabilized O₂ adsorption in a redox-active metal–organic framework. Nature communications, 11(1), Article 3087. https://doi.org/10.1038/s41467-020-16897-z

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abstract = "The design of stable adsorbents capable of selectively capturing dioxygen with a high reversible capacity is a crucial goal in functional materials development. Drawing inspiration from biological O2 carriers, we demonstrate that coupling metal-based electron transfer with secondary coordination sphere effects in the metal–organic framework Co2(OH)2(bbta) (H2bbta = 1H,5H-benzo(1,2-d:4,5-d′)bistriazole) leads to strong and reversible adsorption of O2. In particular, moderate-strength hydrogen bonding stabilizes a cobalt(III)-superoxo species formed upon O2 adsorption. Notably, O2-binding in this material weakens as a function of loading, as a result of negative cooperativity arising from electronic effects within the extended framework lattice. This unprecedented behavior extends the tunable properties that can be used to design metal–organic frameworks for adsorption-based applications.",

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AU - Darago, Lucy E.

AU - Trump, Benjamin A.

AU - Bernales, Varinia

AU - Li, Harriet

AU - Colwell, Kristen A.

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AU - Brown, Craig M.

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AB - The design of stable adsorbents capable of selectively capturing dioxygen with a high reversible capacity is a crucial goal in functional materials development. Drawing inspiration from biological O2 carriers, we demonstrate that coupling metal-based electron transfer with secondary coordination sphere effects in the metal–organic framework Co2(OH)2(bbta) (H2bbta = 1H,5H-benzo(1,2-d:4,5-d′)bistriazole) leads to strong and reversible adsorption of O2. In particular, moderate-strength hydrogen bonding stabilizes a cobalt(III)-superoxo species formed upon O2 adsorption. Notably, O2-binding in this material weakens as a function of loading, as a result of negative cooperativity arising from electronic effects within the extended framework lattice. This unprecedented behavior extends the tunable properties that can be used to design metal–organic frameworks for adsorption-based applications.

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