Elongated‐Geminiarene: Syntheses, Solid‐State Conformational Investigations, and Application in Aromatics/Cyclic Aliphatics Separation

Abstract Energy‐saving separation and purification of industrially important compounds with similar physical and chemical properties by novel molecular crystalline materials are of great importance and highly desired. Here a newly enlarged version of geminiarene, namely elongated‐geminiarene (ElGA), is first designed and synthesized. Taking advantages of both geminiarenes and biphenarenes, ElGA shows great features including scalable synthesis, nanometer‐sized cavity, rich blend of conformational features, and excellent solid‐state host–guest properties. Significantly, the functional crystalline materials of ElGA are highly effective in the separation of aromatics and cyclic aliphatics, showing a preference for dimethylbenzene over its corresponding hydrogenation products and paving a new avenue for separation science and industry.