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)₃]²⁺ (bpy = 2,2′-bipyridine) serving as an iconic example. We report the use of the [Ru(bpy)₂]²⁺ fragment as a 90° acceptor tecton (M) in coordination-driven self-assembly to synthesize a M₄L₄ metallacycle (L = 4,4′-bipyridine) and a M₆L₄ truncated tetrahedral cage [L = 2,4,6-tris(4-pyridyl)-1,3,5-triazine]. The M₆L₄ 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^III/II reduction events, with a cathodic shift of the first reduction relative to that of [Ru(bpy)₃]Cl₂ (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)₃]Cl₂. 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.