Highly Selective Separation of Isopropylbenzene and α-Methylstyrene by Nonporous Adaptive Crystals of Perbromoethylated Pillararene via Vapor- and Liquid-Phase Adsorptions

Isopropylbenzene (IPB) and α-methylstyrene (AMS), two members of C9 aromatics, are important in both industrial production and laboratory research, but the separation of IPB/AMS mixtures is still a big challenge. Here, we provide a new strategy to separate IPB and AMS using nonporous adaptive crystals of four pillararenes, perethylated pillar[5]­arene, perethylated pillar[6]­arene, perbromoethylated pillar[5]­arene, and perbromoethylated pillar[6]­arene (BrP6). Among them, BrP6 selectively adsorbs IPB from an equal volume mixture of IPB and AMS with >95% purity for solid–vapor phase adsorption and >94% purity for solid–liquid phase adsorption, while the selectivities for the other three pillararenes are unsatisfactory. Single-crystal structural analyses combined with powder X-ray diffraction and differential scanning calorimetry experiments demonstrate that the selectivity arises from the different stabilities of guest-loaded BrP6 crystals. Moreover, the reversible transitions between guest-free and IPB-loaded structures indicate the preeminent recycling performance of BrP6 crystals.