Coordination-Driven Self-Assembly of Ruthenium Polypyridyl Nodes Resulting in Emergent Photophysical and Electrochemical Properties.

Ruthenium polypyridyl complexes are among the most studied molecular species for photochemical applications such as light-harvesting and photocatalysis, with [Ru(bpy)] (bpy = 2,2'-bipyridine) serving as an iconic example. We report the use of the [Ru(bpy)] fragment as a 90° acceptor tecton (M) in coordination-driven self-assembly to synthesize a ML metallacycle (L = 4,4'-bipyridine) and a ML truncated tetrahedral cage [L = 2,4,6-tris(4-pyridyl)-1,3,5-triazine]. The ML cage possesses emergent properties attributed to its unique electronic structure, which results in increased visible-light absorption and an emission band that decays biexponentially with times of 3 and 790 ns. The presence of multiple ruthenium centers in the cage results in multiple Ru reduction events, with a cathodic shift of the first reduction relative to that of [Ru(bpy)]Cl (0.56 V vs 1.05 V). The ligand-centered reduction shifts anodically (-1.29 vs -1.64 V) versus the first bpy reduction observed in the parent [Ru(bpy)]Cl. The photophysical properties are explained by the existence of two localized charge-transfer states in the cage molecule: one that draws upon the bipyridine π* orbitals and the other upon the 2,4,6-tris(4-pyridyl)-1,3,5-triazine π* orbitals.