Sato Nobuhiro, Toyoda Ryojun, Sato Tetsu, Lang Goo Zi, Takaishi Shinya, Chida Koki, Yoshii Takeharu, Nishihara Hirotomo, Sugimoto Kunihisa, Sakamoto Ryota
Department of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aza-Aoba, Aramaki, Sendai 980-8578, Japan.
Department of Chemistry, Kindai University, 3-4-1 Kowakae, Higashi-Osaka, Osaka 577-8502, Japan.
Precis Chem. 2024 Jun 12;2(9):480-487. doi: 10.1021/prechem.4c00036. eCollection 2024 Sep 23.
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.
微孔分子晶体因其可设计的孔隙率以及对化学和其他刺激的耐受性而成为有前景的材料。在此,我们利用卟啉与富勒烯分子之间的特定相互作用开发了微孔分子共晶体。单晶X射线衍射分析表明,一个镍(II)卟啉与两个富勒烯分子相互作用,形成具有重叠堆积模式的二维蜂窝状网络,提供一维空隙通道。通过热处理或机械研磨激活孔隙后,制备的共晶体可以可逆地纳入气体和溶剂分子,同时保持其单晶性。此外,在水、酸碱或高压存在的情况下,它仍保持其单晶性。本研究中的这些发现扩展了基于分子间相互作用的分子晶体作为多孔材料的可用性,预计这些材料将在其他基于分子的多孔材料无法适用的条件下发挥作用。