Department of Organic and Polymer Chemistry, College of Chemistry and Chemical Engineering, Central South University , Changsha, Hunan 410083, China.
J Am Chem Soc. 2018 Feb 21;140(7):2555-2561. doi: 10.1021/jacs.7b10707. Epub 2018 Feb 6.
Discrete spherical metallo-organic capsules at the nanometer scale, especially those constructed from unique building blocks, have received significant attention recently because of their fascinating molecular aesthetics and potential applications due to their compact cavities. Here, the synthesis and characterization of a hexapodal, branched terpyridine ligand are presented along with the nearly quantitative self-assembly of the resulting tetrameric metallo-nanosphere. This metallo-nanosphere exhibited four quasi-triangular and six rhombus-like facets, all of which were made by the same hook-like bis-terpyridine. Collision-induced dissociation experiments were done to investigate overall stability. The metallo-architecture and host-guest chemistry were investigated with coronene and fully characterized by 1D and 2D NMR, ESI-MS, and transmission electron microscopy. Furthermore, this metallo-nanosphere was observed to hierarchically self-assemble into berry-type structures in an acetonitrile/methanol mixture, by virtue of counterion-mediated attractions. The functional molecular metallo-nanosphere presented here expands the reach of terpyridine coordination systems into molecular containers and other model systems.
离散的纳米尺度球形金属有机胶囊，特别是那些由独特的结构单元构建的胶囊，由于其迷人的分子美学和紧凑空腔的潜在应用而受到了极大的关注。在这里，我们介绍了一种六足支化的三联吡啶配体的合成和表征，以及由此得到的四聚金属纳米球的近乎定量的自组装。该金属纳米球呈现出四个准三角形和六个菱形的面，所有这些面都是由相同的钩状双三联吡啶构成的。进行了碰撞诱导解离实验以研究整体稳定性。利用蒄和全氟萘烷对金属结构和主体-客体化学进行了研究，并通过一维和二维 NMR、ESI-MS 和透射电子显微镜进行了全面表征。此外，还观察到这种金属纳米球在乙腈/甲醇混合溶剂中通过抗衡离子介导的吸引力，自组装成浆果状结构。这里展示的功能分子金属纳米球将三联吡啶配位体系的应用范围扩展到了分子容器和其他模型体系中。
