4 years ago

Supersnowflakes: Stepwise Self-Assembly and Dynamic Exchange of Rhombus Star-Shaped Supramolecules

Supersnowflakes: Stepwise Self-Assembly and Dynamic Exchange of Rhombus Star-Shaped Supramolecules
Hai-Bo Yang, Ming Wang, R. Alexander Reese, Olapeju Bolarinwa, Heng Wang, Xu Wang, Xu-Qing Wang, Bo Song, Xiaopeng Li, Jianfeng Cai, Yiming Li, Zhe Zhang, Bingqian Xu, Changlin Liu, Tong Zhang
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.

Publisher URL: http://dx.doi.org/10.1021/jacs.7b01326

DOI: 10.1021/jacs.7b01326

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