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
StatePublished - 2017