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 ³ MLCT excited state over the investigated range of temperatures. For all complexes, deactivation via the ³ MC 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 ( T _pp ) 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 T _pp .