One-Pot Self-Assembly of Stellated Metallosupramolecules from Multivalent and Complementary Terpyridine-Based Ligands

A series of stellated metallosupramolecular architectures have been assembled through three-component integrative self-sorting. Building on the complementary ligand pairing, the initial attempts to synthesize the hexagram complex from a combination of X-shaped tetrakis- and V-shaped bis-terpyridine ligands, and Cd^II ions, resulted in an unprecedented mixture of stellated octanuclear and dodecanuclear metallocages, which were further isolated by column chromatography. To overcome the unexpected obstacle, the multivalent ligand design along with spontaneous heteroleptic complexation was applied to realization of the one-pot synthesis of the intricate topology. A centrally situated triangle served as a prop for quantitative formation of the six-pointed stellated complex. Notably, in the absence of the triangular prop, a four-pointed star was produced.