Multicomponent Self‐Assembly of Metallo‐Supramolecular Macrocycles and Cages through Dynamic Heteroleptic Terpyridine Complexation

Spontaneous formation of the heteroleptic cadmium(II) bis(terpyridine) complex under ambient conditions can be achieved by a combination of 6,6′′‐di(2,6‐dimethoxylphenyl)‐substituted and unsubstituted terpyridine‐based ligands. Building on this dynamic heteroleptic complexation, diverse metallo‐supramolecular macrocycles and cages were readily assembled in quantitative yields from the predesigned multicomponent systems. The complementary ligation reinforced self‐recognition to facilitate the shape‐dependent self‐sorting of a four‐component dynamic library into two well‐defined parallelograms. In addition, the subtle lability difference between homoleptic and heteroleptic complexes led to the site‐selective Cd II –Zn II transmetalation in the Sierpiński triangle. Facile construction of a dodecanuclear tetrahedral metallocage was also realized by using two self‐recognizable tritopic building blocks. The photophysical study of the metallo‐supramolecules assembled from the d 10 metal ions revealed intense ligand‐based photoluminescence in solution. The self‐assembly strategy described here provides an efficient methodology for building pre‐programmable, sophisticated supramolecular architectures furnished with photoactivity.