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

Zhenzhong Lu, Harry Godfrey, Ivan Da Silva, Yongqiang Cheng, Mathew Savage, Floriana Tuna, Eric Mcinnes, Simon J. Teat, Kevin J. Gagnon, Mark D. Frogley, Pascal Manuel, Svemir Rudić, Anibal J. Ramirez-Cuesta, Timothy L. Easun, Sihai Yang, Martin Schroder

    Research output: Contribution to journalArticlepeer-review


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


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