Electrostatic Potential Matching in an Anion‐Pillared Framework for Benchmark Hexafluoroethane Purification from Ternary Mixture

One‐step purification of CF3CF3 from ternary CF3CH2F/CF3CHF2/CF3CF3 mixture is crucial since its vital role in the semiconductor industry. However, efficient separation of chemically inert CF3CF3 remains challenging due to the difficulty in creating specific recognition sites in porous materials. In this work, we report the first example of anion‐pillared MOFs to the separation of fluorinated electronic specialty gases, utilizing the unique electrostatic potential matching in the bipolar pores of SIFSIX‐1‐Cu to realize a benchmark CF3CH2F/CF3CHF2/CF3CF3 separation. SIFSIX‐1‐Cu exhibits the highest CF3CH2F and CF3CHF2 adsorption capacity at 0.01 bar, as well as the highest CF3CH2F/CF3CF3 and CF3CHF2/CF3CF3 IAST selectivity. Additionally, high‐purity (≥ 99.995%) CF3CF3 with record productivity (882.9 L/kg) can be acquired through one‐step breakthrough experiment of CF3CH2F/CF3CHF2/CF3CF3 (5/5/90). Theoretical calculations further reveal that the coexistence of electronegative SiF62‐ and partially electropositive H sites promotes SIFSIX‐1‐Cu to effectively anchor CF3CH2F and CF3CHF2 through multiple supramolecular interactions.