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

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(V^III) {[V^III₂(OH)₂(L)], LH₄=biphenyl-3,3',5,5'-tetracarboxylic acid} can be oxidized to isostructural MFM-300(V^IV), [V^IV₂O₂(L)], in which deprotonation of the bridging hydroxyl groups occurs. MFM-300(V^III) 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(V^IV) 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.