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of pore window size is the standard approach for tuning gas selectivity in
porous solids. Here, we present the first example where this is translated into
a molecular porous liquid formed from organic cage molecules. Reduction of the
cage window size by chemical synthesis switches the selectivity from
Xe-selective to CH4-selective, which is understood using 129Xe,
1H, and pulsed-field gradient NMR spectroscopy.