Vertical Assembly of Giant Double‐ and Triple‐Decker Spoked Wheel Supramolecular Structures

: The double- or triple-decker 3D metallo-hexagons were obtained by self-assembly of multitopic tris-terpyridines with Cd2+ ions in near-quantitative yield. Comprising up to 72 ionic pairs, the multiple spoked wheels display characteristic reversible gelation properties under thermodynamic conditions. The supramolecular metallo-nanoarchitectures were characterized by 1 H NMR, 2D NMR (COSY and NOESY), and diffusion-ordered spectroscopy (DOSY) and HR-ESI-MS, traveling-wave ion mobility mass spectrometry (TWIM-MS), TEM, and AFM. For the first time, the self-assembly of 45 units at once was demonstrated to yield exceptional giant triple-decker hexagons of up to circa 42 000 Da.