Modulating Supramolecular Binding of Carbon Dioxide in a Redox-Active Porous Metal-Organic Framework

Research output: Contribution to journalArticle

  • External authors:
  • Zhenzhong Lu
  • Harry Godfrey
  • Ivan Da Silva
  • Yongqiang Cheng
  • Mathew Savage
  • Simon J. Teat
  • Kevin J. Gagnon
  • Mark D. Frogley
  • Pascal Manuel
  • Svemir Rudić
  • Anibal J. Ramirez-Cuesta
  • Timothy L. Easun


Hydrogen bonds dominate many chemical and biological processes, and chemical modification enables control and modulation of host–guest systems. Here we report a targeted modification of hydrogen bonding and its effect on guest binding in redox-active materials. MFM-300(VIII) {[VIII2(OH)2(L)], LH4=biphenyl-3,3′,5,5′-tetracarboxylic acid} can be oxidized to isostructural MFM-300(VIV), [VIV2O2(L)], in which deprotonation of the bridging hydroxyl groups occurs. MFM-300(VIII) shows the second highest CO2 uptake capacity in metal-organic framework materials at 298 K and 1 bar (6.0 mmol g−1) and involves hydrogen bonding between the OH group of the host and the O-donor of CO2, which binds in an end-on manner, OH... OCO2 =1.863(1) Å. In contrast, CO2-loaded MFM-300(VIV) shows CO2 bound side-on to the oxy group and sandwiched between two phenyl groups involving a unique OCO2···c.g.phenyl interaction [3.069(2), 3.146(3) Å]. The macroscopic packing of CO2 in the pores is directly influenced by these primary binding sites.

Bibliographical metadata

Original languageEnglish
Article number14212
JournalNature Communications
Early online date13 Feb 2017
Publication statusPublished - 2017

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