日本东京大学Makoto Fujita团队近日取得一项新成果。经过不懈努力，他们的最新研究提出了超分子配位笼通过对称失配策略作为结晶海绵。这一研究成果发表在2025年3月5日出版的国际学术期刊《自然—化学》上。

在这项研究中，课题组解决了其中的一些局限性，将钯基八面体M₆L₄（T_d）配位笼作为结晶海绵。促进笼型结晶的关键是加入大的芳香聚磺酸盐（“粘合”阴离子）；配位笼和粘合阴离子之间的对称不匹配（D_2h）导致低对称空间群（P1），防止了客体紊乱并导致晶体中客体可达通道的形成。客体分子可以封装之前或之后笼结晶。该空腔的大小和主客体性质使其能够分析广泛的化合物，包括水溶性分子、大的两亲分子（分子量约为1200）和分子聚集体。课题组研究人员已经展示了“配位笼-粘合剂”策略的多功能性，通过将其应用于三增三角形棱镜形状的M₉L₆笼，将客体范围扩展到中型药物分子。

研究人员表示，晶体海绵法能够对单晶多孔材料中吸收的客体分子进行单晶X射线衍射分析。然而，它在大型或高极性客体中的应用仍然具有挑战性。

附：英文原文

Title: Supramolecular coordination cages as crystalline sponges through a symmetry mismatch strategy

Author: He, Wei, Yu, Yikuan, Iizuka, Kenta, Takezawa, Hiroki, Fujita, Makoto

Issue&Volume: 2025-03-05

Abstract: The crystalline sponge method enables single-crystal X-ray diffraction analysis of guests absorbed within single-crystalline porous materials. However, its application with large or highly polar guests remains challenging. In this study, we addressed some of these limitations using palladium-based octahedron-shaped M₆L₄ (T_d) coordination cages as crystalline sponges. The key to facilitate the crystallization of the cage is the addition of large aromatic polysulfonates (‘sticker’ anions); the symmetry mismatch between the cage and the sticker (D_2h) results in a low-symmetry space group (P1), preventing guest disorder and leading to the formation of guest-accessible channels in the crystal. Guests can be encapsulated either before or after cage crystallization. The size and host–guest properties of the cavity enable analysis of a broad range of compounds, including water-soluble molecules, large amphiphilic molecules (molecular weight of ~1,200) and molecular aggregates. We have demonstrated the versatility of the cage–sticker strategy through its application to a triaugmented triangular-prism-shaped M₉L₆ cage, extending the guest scope to medium-sized pharmaceutical molecules.

DOI: 10.1038/s41557-025-01750-x

Source: https://www.nature.com/articles/s41557-025-01750-x