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

Research output: Contribution to journalArticle

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 languageEnglish (US)
Article number3087
JournalNature communications
Volume11
Issue number1
DOIs
StatePublished - Dec 1 2020

PubMed: MeSH publication types

  • Journal Article
  • Research Support, U.S. Gov't, Non-P.H.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), [3087]. https://doi.org/10.1038/s41467-020-16897-z