Synergistic global and local flexibilities in Zr-based metal–organic frameworks enable sequential sieving of hexane isomers

Separating hexane isomers based on the branching degree is crucial for their efficient utilization in the petrochemical industry, yet remains challenging due to their similar properties. Here we report a temperature-responsive Zr-based metal-organic framework, Zr-fum-FA, capable of sequentially sieving linear, mono-, and di-branched hexane isomers. Notably, the pore structure of Zr-fum-FA dynamically transforms from segmented triangular channels to an integrated rhombic configuration as the temperature increases, leading to distinct sieving effects. At low temperatures, the narrow triangular pores allow the exclusive adsorption of <i>n</i>-hexane while excluding branched isomers. In contrast, the expanded rhombic pores at high temperatures enable the sieving of mono- and di-branched isomers. Mechanistic studies reveal that this unique dual-sieving behavior originates from the synergistic effects of the global framework flexibility and the local dynamics of pendent hydroxyl groups. Furthermore, we demonstrate the decoupling of global and local flexibilities <i>via</i> two strategies: incorporating steric hindrance to dampen the global framework dynamics and enhancing the metal node rigidity to limit the local vibrations. These findings not only provide a promising adsorbent for the challenging separation of hexane isomers but also offer rational design principles for harnessing flexibility in MOFs.