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Modulating supramolecular binding of carbon dioxide in a redox-active porous metal-organic framework.

  • Author(s): Lu, Zhenzhong;
  • Godfrey, Harry GW;
  • da Silva, Ivan;
  • Cheng, Yongqiang;
  • Savage, Mathew;
  • Tuna, Floriana;
  • McInnes, Eric JL;
  • Teat, Simon J;
  • Gagnon, Kevin J;
  • Frogley, Mark D;
  • Manuel, Pascal;
  • Rudić, Svemir;
  • Ramirez-Cuesta, Anibal J;
  • Easun, Timothy L;
  • Yang, Sihai;
  • Schröder, Martin
  • et al.
Abstract

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, =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 ···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.

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