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Herein, we report the formation of multinuclear Ir 4 , Ir 6 , and Ir 12 supramolecular complexes via the bridge-driven self-assembly of tetrazolyl ligands. The synthesis of dimeric half-sandwich Ir units was made by the reaction of half-sandwich Ir units and tetrazolyl ligands in a molar ratio of 1:2. The use of different ligands containing multiple tetrazolyl units resulted in the formation of different Ir supramolecular architectures. The reaction of [Cp*IrCl 2 ] 2 , AgOTf, and 1,2- or 1,3-ditetrazolyl benzene in a molar ratio of 1:3:1 resulted in the formation of rectangular tetranuclear or truncated trigonal pyramidal hexanuclear Ir complexes, respectively. On the other hand, the reaction of [Cp*IrCl 2 ] 2 , AgOTf, and 1,3,5-tritetrazolyl benzene in a molar ratio of 6:18:4 produced a supramolecular dodecanuclear iridium complex. The molecular structure of the complex resembled a truncated tetrahedral structure with a large inner cavity, as determined by X-ray crystallography.

Tetra-, Hexa-, Dodeca-Nuclear Ir Supramolecules via Bridge-Driven Self-Assembly of Tetrazolyl Ligands