Hexagon wreaths: Self-assembly of discrete supramolecular fractal architectures using multitopic terpyridine ligands

In this study, we overcame a challenge in conventional self-assembly of macrocycles that uses ditopic 2,2:6,2-terpyridine (tpy) building blocks with a 120angle between two ligating moieties, which generally produces a mixture of multiple macrocycles instead of a single hexagon. Two supramolecular hexagon wreaths, [Zn₉LA₆] and [Zn₁₂LB₆], were designed and self-assembled from tritopic and tetratopic tpy ligands with Zn(II) ions, respectively. These multitopic ligands, bearing multiple binding sites, increased the total density of coordination sites and provided high geometric constraints to induce the formation of discrete structures. Such hexagon wreaths, which were constructed by simple recursion of small hexagons around a central hexagon, exhibit fractal geometry features with self-similarity at different levels. The shapes, sizes, and structures were fully characterized by NMR, ESI-MS, traveling-wave ion mobility mass spectrometry (TWIM-MS), and transmission electron microscopy. With diameters around 5.5 nm for [Zn ₉LA₆] and 5.8 nm for [Zn₁₂LB₆], the remarkable rigidity of these fractal architectures was supported by TWIM-MS, in contrast to the high flexibility of macrocycles assembled by ditopic tpy ligands.