Separation of Cyclohexanone and Cyclohexanol by Adaptive Pillar[5]arene Cocrystals Accompanied by Vapochromic Behavior

The separation of cyclohexanone (CHA-one) and cyclohexanol (CHA-ol) mixtures is of great importance in the chemical industry. Current technology exploits multiple steps of energy-intensive rectification due to their close boiling points. Herein, we report a new and energy-efficient adsorptive separation method employing binary adaptive macrocycle cocrystals (MCCs) built with π-electron-rich pillar[5]arene (P5) and an electron-deficient naphthalenediimide derivative (NDI) that can selectively separate CHA-one from an equimolar CHA-one/CHA-ol mixture with >99% purity. Intriguingly, this adsorptive separation process is accompanied by vapochromic behavior from pink to dark brown. Single-crystal and powder X-ray diffraction analyses reveal that the adsorptive selectivity and vapochromic property are derived from the CHA-one vapor inside the cocrystal lattice voids triggering solid-state structural transformations to yield charge-transfer (CT) cocrystals. Moreover, the reversible transformations make the cocrystalline materials highly recyclable.