Ultra‐Tuning of the Rare‐Earth fcu‐MOF Aperture Size for Selective Molecular Exclusion of Branched Paraffins

Using isoreticular chemistry allows the design and construction of a new rare‐earth metal (RE) fcu ‐MOF with a suitable aperture size for practical steric adsorptive separations. The judicious choice of a relatively short organic building block, namely fumarate, to bridge the 12‐connected RE hexanuclear clusters has afforded the contraction of the well‐defined RE‐ fcu ‐MOF triangular window aperture, the sole access to the two interconnected octahedral and tetrahedral cages. The newly constructed RE (Y³⁺ and Tb³⁺) fcu ‐MOF analogues display unprecedented total exclusion of branched paraffins from normal paraffins. The resultant window aperture size of about 4.7 Å, regarded as a sorbate‐size cut‐off, enabled a complete sieving of branched paraffins from normal paraffins. The results are supported by collective single gas and mixed gas/vapor adsorption and calorimetric studies.