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Open Access Publications from the University of California

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

  • Author(s): Lu, Z
  • Godfrey, HGW
  • Da Silva, I
  • Cheng, Y
  • Savage, M
  • Tuna, F
  • McInnes, EJL
  • Teat, SJ
  • Gagnon, KJ
  • Frogley, MD
  • Manuel, P
  • Rudić, S
  • Ramirez-Cuesta, AJ
  • Easun, TL
  • Yang, S
  • Schröder, M
  • et al.

© 2017 The Author(s). 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 CO2uptake 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 CO2bound side-on to the oxy group and sandwiched between two phenyl groups involving a unique OCO2···c.g.phenylinteraction [3.069(2), 3.146(3) Å]. The macroscopic packing of CO2in the pores is directly influenced by these primary binding sites.

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