Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, School of Chemistry, Central China Normal University , Wuhan, Hubei 430079, China.
Department of Chemistry, University of South Florida , Tampa, Florida 33620, United States.
J Am Chem Soc. 2017 Jun 21;139(24):8174-8185. doi: 10.1021/jacs.7b01326. Epub 2017 Jun 8.
With the goal of increasing the complexity of metallo-supramolecules, two rhombus star-shaped supramolecular architectures, namely, supersnowflakes, were designed and assembled using multiple 2,2':6',2″-terpyridine (tpy) ligands in a stepwise manner. In the design of multicomponent self-assembly, ditopic and tritopic ligands were bridged through Ru(II) with strong coordination to form metal-organic ligands for the subsequent self-assembly with a hexatopic ligand and Zn(II). The combination of Ru(II)-organic ligands with high stability and Zn(II) ions with weak coordination played a key role in the self-assembly of giant heteroleptic supersnowflakes, which encompassed three types of tpy-based organic ligands and two metal ions. With such a stepwise strategy, the self-sorting of individual building blocks was prevented from forming the undesired assemblies, e.g., small macrocycles and coordination polymers. Furthermore, the intra- and intermolecular dynamic exchange study of two supersnowflakes by NMR and mass spectrometry revealed the remarkable stability of these giant supramolecular complexes.
为了增加金属超分子的复杂性，设计并通过逐步组装两种菱形星形超分子结构，即超级雪花，使用多个 2,2':6',2″-三联吡啶（tpy）配体。在多组分自组装的设计中，通过 Ru(II) 桥接双齿和三齿配体，以形成金属有机配体，然后与六齿配体和 Zn(II) 进行后续自组装。高稳定性的 Ru(II)-有机配体与弱配位的 Zn(II) 离子在巨型杂轮超雪花的自组装中发挥了关键作用，其中包含三种基于 tpy 的有机配体和两种金属离子。通过这种逐步策略，可以防止单个构建块的自分类形成不需要的组装体，例如小的大环和配位聚合物。此外，通过 NMR 和质谱对两个超级雪花的分子内和分子间动态交换研究揭示了这些巨大的超分子配合物的显著稳定性。
