MLCT Excited-State Behavior of Trinuclear Ruthenium(II) 2,2'-Bipyridine Complexes.

Four trinuclear ruthenium(II) polypyridyl complexes were synthesized, and a detailed investigation of their excited-state properties was performed. The tritopic sexi-pyridine bridging ligands were obtained via para or meta substitution of a central 2,2'-bipyridine fragment. A para connection between the 2,2'-bipyridine chelating moieties of the bridging ligand led to a red-shifted MLCT absorption band in the visible part of the spectra, whereas the meta connection induced a broadening of the LC transitions in the UV region. A convergent energy transfer from the two peripheral metal centers to the central Ru(II) moiety was observed for all trinuclear complexes. These complexes were in thermal equilibrium with an upper-lying 3MLCT excited state over the investigated range of temperatures. For all complexes, deactivation via the 3MC excited state was absent at room temperature. Importantly, the connection in the para position for both central and peripheral 2,2'-bipyridines of the bridging ligand resulted in a trinuclear complex (Tpp) that absorbed more visible light, had a longer-lived excited state, and had a higher photoluminescence quantum yield than the parent [Ru(bpy)3]2+, despite its red-shifted photoluminescence. This behavior was attributed to the presence of a highly delocalized excited state for Tpp.