Adaptive Induced‐Fit via Engineered Linker Regioisomerization in Biomimetic Zeolitic Imidazolate Frameworks for Boosting SF 6 /N 2 Separation

Capturing and recovering sulfur hexafluoride (SF 6 ) is a crucial yet formidable challenge in mitigating global warming. Herein, we propose a programmable linker regioisomerization strategy within zeolitic imidazolate frameworks (ZIFs) to modulate their stimulus‐responsive structural flexibility, thereby significantly enhancing SF 6 capture efficiency from nitrogen (N 2 ) streams. Simultaneous regioisomerization of the methyl group in ZIF‐8 and the aldehyde group in ZIF‐90 on the imidazolate linkers yields ZIF‐94, which exhibits a rare guest‐induced reversible framework deformation upon SF 6 adsorption. This behavior confers an enzyme‐like induced‐fit recognition mechanism for SF 6 molecules, strengthening host–guest interactions. As a result, ZIF‐94 achieves a high SF 6 adsorption capacity of 1.97 mmol g −1 and an ultrahigh SF 6 stacking density of 1438.69 mg cm −3 at 298 K and 0.1 bar, along with dramatically enhanced SF 6 /N 2 selectivities over ZIF‐8 and ZIF‐90. In situ experiments and theoretical analyses reveal that the SF 6 ‐induced structural flexibility of ZIF‐94 allows the framework to dynamically adjust and optimize its cage structure to match gas molecules, thus leading to significantly reinforced SF 6 /N 2 separation performance. The experimental column breakthrough tests and pressure swing adsorption simulations confirm the practical separation performance for SF 6 /N 2 mixtures in ZIF‐94. This work offers useful insights for designing flexible adsorbents for gas separation applications.