Russian-Doll-Like Molecular Cubes.
Die LiuKaixiu LiMingzhao ChenTingting ZhangZhengguang LiJia-Fu YinLipeng HeJun WangPanchao YinYi-Tsu ChanPingshan WangPublished in: Journal of the American Chemical Society (2020)
Nanosized cage-within-cage compounds represent a synergistic molecular self-assembling form of three-dimensional architecture that has received particular research focus. Building multilayered ultralarge cages to simulate complicated virus capsids is believed to be a tough synthetic challenge. Here, we synthesize two large double-shell supramolecular cages by facile self-assembly of presynthesized metal-organic hexatopic terpyridine ligands with metal ions. Differing from the mixture of prisms formed from the inner tritopic ligand, the redesigned metal-organic hexatopic ligands bearing high geometric constraints that led to the exclusive formation of discrete double-shell structures. These two unique nested cages are composed of inner cubes (5.1 nm) and outer huge truncated cubes (12.0 and 13.2 nm) with six large bowl-shape subcages distributed on six faces. The results with molecular weights of 75 232 and 77 667 Da were among the largest synthetic cage-in-cage supramolecules reported to date. The composition, size and shape were unambiguously characterized by a combination of 1H NMR, DOSY, ESI-MS, TWIM-MS, TEM, AFM, and SAXS. This work provides an interesting model for functional recognition, delivery, and detection of various guest molecules in the field of supramolecular materials.