Coordination flexibility aided CO2‐specific gating in an Iron Isonicotinate MOF

Coordination flexibility assisted porosity has been introduced into an Iron-isonicotinate metal organic framework (MOF), (Fe(4-PyC) 2 .(OH). The framework showed CO 2 -specific gate opening behavior, which gets tuned as a function of temperature and pressure. The MOF's physisorptive porosity towards CO 2 , CH 4 , and N 2 was investigated; it adsorbed only CO 2 via a gate opening phenomenon. The isonicotinate, representing a borderline soft base, is bound to the hard Fe 3+ centre through monodentate carboxylate and pyridyl nitrogen. This moderately weak binding enables isonicotinate to spin like a spindle under the CO 2 pressure opening the gate for a sharp increase in CO 2 uptake at 333 mmHg (At 298K, the CO 2 uptake increases from 0.70 to 1.57 mmol/g). We investigated the MOF's potential for CO 2 /N 2 and CO 2 /CH 4 gas separation aided by this gating. IAST model reveals that the CO 2 /N 2 selectivity jumps from 325 to 3131 when the gate opens, while the CO 2 /CH 4 selectivity increases three times. Interestingly, this Fe-isonicotinate MOF did not follow the trend set by our earlier reported Hard-Soft Gate Control (established for isostructural M 2+ -isonicotinate MOFs (M = Mg, Mn)). However, we account for this discrepancy using the different oxidation state of metals confirmed by X-ray photoelectron spectroscopy and magnetism.

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