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Microporous molecular crystals are promising materials because of their designable porosity as well as their resistance to chemical and other stimuli. Here, we developed microporous molecular cocrystals by taking advantage of the specific interactions between porphyrins and fullerene molecules. Single-crystal X-ray diffraction analysis revealed that one nickel(II) porphyrin interacts with two fullerene molecules to form a two-dimensional honeycomb network with an eclipsed stacking mode, providing one-dimensional void channels. After the pores were activated by heat treatment or mechanical grinding, the prepared cocrystal can incorporate gas and solvent molecules reversibly while maintaining its single-crystallinity. Also, it retained its single-crystallinity in the presence of water, acid–base, or high pressure. These findings in this study expand the availability of molecular crystals based on intermolecular interactions as porous materials, which are expected to work under conditions that have not been applicable to other molecule-based porous materials.
Sato et al. (Wed,) studied this question.