Scholarlink

<p>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 M<sub>6</sub>L<sub>4</sub> (<i>T</i><sub><i>d</i></sub>) 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 (<i>D</i><sub>2<i>h</i></sub>) results in a low-symmetry space group (<i>P</i><InlineEquation ID="IEq1"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="41557_2025_1750_Article_IEq1.gif" Format="GIF" Height="16" Rendition="HTML" Resolution="72" Type="Linedraw" Width="10" /> </InlineMediaObject> <EquationSource Format="TEX">\(\bar{1}\)</EquationSource> <EquationSource Format="MATHML"><math> <mover accent="true"> <mrow> <mn>1</mn> </mrow> <mo>¯</mo> </mover> </math></EquationSource> </InlineEquation>), 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 M<sub>9</sub>L<sub>6</sub> cage, extending the guest scope to medium-sized pharmaceutical molecules.</p><p></p>

错误：搜索内容不能为空，请输入英文关键词
错误：关键词超出字数限制，请精简
高级检索

Supramolecular coordination cages as crystalline sponges through a symmetry mismatch strategy

  • 期刊论文

  • 发表日期：

    2025年3月5日

查看全文
  • Wei He,
  • Yikuan Yu,
  • Kenta Iizuka,
  • Hiroki Takezawa,
  • Makoto Fujita

摘要

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 (Td) 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 (D2h) results in a low-symmetry space group (P \(\bar{1}\) 1 ¯ ), 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.