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 and Jeffrey R. Long ()
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Julia Oktawiec: University of California
Henry Z. H. Jiang: University of California
Jenny G. Vitillo: University of Minnesota
Douglas A. Reed: University of California
Lucy E. Darago: University of California
Benjamin A. Trump: Center for Neutron Research
Varinia Bernales: University of Minnesota
Harriet Li: Massachusetts Institute of Technology
Kristen A. Colwell: University of California
Hiroyasu Furukawa: University of California
Craig M. Brown: Center for Neutron Research
Laura Gagliardi: University of Minnesota
Jeffrey R. Long: University of California

Nature Communications, 2020, vol. 11, issue 1, 1-11

Abstract: 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.

Date: 2020
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DOI: 10.1038/s41467-020-16897-z

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