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

  • Author(s): Oktawiec, Julia;
  • Jiang, Henry ZH;
  • 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
  • et al.
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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