Negative cooperativity upon hydrogen bond-stabilized O 2 adsorption in a redox-active metal-organic framework

• Published in: Nature communications 2020-06, Vol.11 (1), p.3087
• Main Authors: Oktawiec, Julia, Jiang, Henry Z H, Vitillo, Jenny G, Reed, Douglas A, Darago, Lucy E, Trump, Benjamin A, Bernales, Varinia, Li, Harriet, Colwell, Kristen A, Furukawa, Hiroyasu, Brown, Craig M, Gagliardi, Laura, Long, Jeffrey R
• Format: Article
• Language: English
• ISSN: 2041-1723
• DOI: 10.1038/s41467-020-16897-z

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 O carriers, we demonstrate that coupling metal-based electron transfer with secondary coordination sphere effects in the metal-organic framework Co (OH) (bbta) (H bbta = 1H,5H-benzo(1,2-d:4,5-d')bistriazole) leads to strong and reversible adsorption of O . In particular, moderate-strength hydrogen bonding stabilizes a cobalt(III)-superoxo species formed upon O adsorption. Notably, O -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.