Giant, Hollow 2D Metalloarchitecture: Stepwise Self-Assembly of a Hexagonal Supramolecular Nut

• Published in: Journal of the American Chemical Society 2016-08, Vol.138 (31), p.10041-10046
• Main Authors: Li, Yiming, Jiang, Zhilong, Wang, Ming, Yuan, Jie, Liu, Die, Yang, Xiaoyu, Chen, Mingzhao, Yan, Jun, Li, Xiaopeng, Wang, Pingshan
• Format: Article
• Language: English
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/jacs.6b06021

A polyterpyridinyl building block-based nutlike hexagonal bismetallo architecture with a central hollow Star of David was assembled by a stepwise strategy. This nanoarchitecture can be viewed as a recursive mathematical form that possesses a supramolecular corner-connected cyclic structure, i.e., a triangle or rhombus at various levels of scale or detail. The key metallo-organic ligand (MOL) with four uncomplexed free terpyridines was obtained by a final Suzuki cross-coupling reaction with a tetrabromoterpyridine Ru dimer. The molecular metallorhombus was prepared by reacting the MOL with a 60° bis-terpyridine and Fe2+. The giant hollow hexagonal nut with a diameter of more than 11 nm and a molecular weight of ca. 33 kDa was obtained in near-quantitative yield by mixing the two types of multi-terpyridine ligands with Fe2+. The supramolecular architecture was characterized by NMR (1H and 13C), 2D NMR (COSY and ROESY), and DOSY spectroscopies, high-resolution electrospray ionization mass spectrometry, traveling-wave ion mobility mass spectrometry, and transmission electron microscopy.