The complex [(PTZpbpy) 2 Ru(dpp)](PF 6 ) 2 coupling a phenothiazine derived electron donor to a ruthenium complex with a polyazine bridging ligand dpp (PTZpbpy=4-methyl-4′-(4-(N-phenothiazinato)pentyl)-2,2′-bipyridine, dpp=2,3-bis(2-pyridyl)pyrazine) has been synthesized and the redox, spectroscopic, and excited state properties elucidated. In the coupled electron donor system, the emission intensity from the Ru(dπ)→dpp(π ∗ ) 3 MLCT state is quenched by 94% of that of the analogous system [(bpy) 2 Ru(dpp)](PF 6 ) 2 (bpy=2,2′-bipyridine) which lacks a coupled electron donor. Coupling a donor–chromophore unit to a bridging ligand will allow the expansion of the molecular architecture to form complex molecular assemblies which contain covalently attached electron donors.