Solvent‐Responsive Nonporous Adaptive Crystals Derived from Pyridinium Hydrochloride and the Application in Iodine Adsorption

Nonporous adaptive crystals (NACs) are crystalline nonporous materials that can undergo a structural adaptive phase transformation to accommodate specific guest via porous cavity or lattice voids. Most of the NACs are based on pillararenes because of their flexible backbone and intrinsic porous structure. Here a readily prepared organic hydrochloride of 4-(4-(diphenylamino)phenyl)pyridin-1-ium chloride (TPAPyH), exhibiting the solvent dimension-dependent adaptive crystallinity is reported. Wherein it forms a nonporous α crystal in a solvent with larger dimensions, while forming two porous β and γ crystals capable of accommodating solvent molecules in solvent with small size. Furthermore, the thermal-induced single-crystal-to-single-crystal (SCSC) transition from the β to α phase can be initiated. Upon exposure to iodine vapor or immersion in aqueous solution, the nonporous α phase transforms to porous β phase by adsorbing iodine molecules. Owing to the formation of trihalide anion I