Tuning the host-guest interactions in a phosphine coordination polymer through different types of post-synthetic modification
Por:
Nuñez A.J., Chang M.S., Ibarra I.A., Humphrey S.M.
Publicada:
1 ene 2014
Resumen:
The porous Phosphine Coordination Material, PCM-10 contains abundant free P(III) donor sites that can be subjected to a variety of post-synthetic modifications. The diverse P(III)/P(V) organic reactivity and coordination chemistry available to aryl phosphines have been exploited to decorate the pores of PCM-10, allowing for an extensive structure-function study. Polar P=O moieties, charged P+-CH3 phosphonium species with exchangeable coanions (I-, F-, BF4 -, and PF6 -) and P-AuCl groups have been successfully post-synthetically incorporated. These modifications directly affect the strength of the resulting host-guest interactions, as demonstrated by comparative sorption studies of CO2, H2, and other gases in the solid-state. Broad tunability of the enthalpy of CO2 adsorption is observed: incorporation of BF4 - ions inside the pores of PCM-10 results in 24% enhancement of the isosteric adsorption enthalpy of CO2 compared to the parent material, while F- anions induce a 36% reduction. Meanwhile, AuCl-decorated PCM-10 shows a high H2 sorption capacity of 4.72 wt % at 77 K and 1.0 bar, versus only 0.63 wt % in the unmodified material. © 2013 American Chemical Society.
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