Continuous Nanospace in Nanoporous Liquid Crystal Investigated by ¹²⁹Xe NMR Spectroscopy

Continuous nanopores within fluid materials could be used for novel chemical events such as the accommodation of guest molecules, unique arrays of the entrapped molecules, and chemical reactions in a dynamic molecular assembly. Columnar liquid crystals composed of a one-dimensionally stacked assembly of shape-persistent macrocycles form nanochannels owing to the intrinsic nanospace in the column. However, the existence of substantial nanoporosity has not been confirmed experimentally thus far. In this study, for the first time in the literature, we confirmed the presence of discrete and spatiotemporally continuous voids in a liquid-crystalline material. In Xe-129 NMR spectroscopy of liquid crystalline columnar assembly of imine-bridged shape-persistent macrocycles under Xe atmosphere, the NMR signals of the Xe atoms entrapped in the liquid-crystalline macrocycle depended on the gas pressure and phase-transition temperatures. These results indicate that the encapsulation of Xe gas molecules within the discrete and oriented nanospaces of nanoporous liquid crystals is different from the homogeneous dissolution of the solute in an ordinary solution.