2017 journal article
Coordination-Driven Self-Assembly of Ruthenium Polypyridyl Nodes Resulting in Emergent Photophysical and Electrochemical Properties
Inorganic Chemistry, 57(7), 3587–3595.
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 RuIII/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.