A pi-extended, redox-active bridging ligand 4',5'-bis(propylthio)tetrathiafulvenyl[i]dipyrido[2,3-a:3',2'-c]phenazin e (L) was prepared via direct Schiff-base condensation of the corresponding diamine-tetrathiafulvalene (TTF) precursor with 4,7-phenanthroline-5,6-dione. Reactions of L with [Ru(bpy)(2)Cl-2] afforded its stable mono- and dinuclear ruthenium(II) complexes 1 and 2. They have been fully characterized, and their photophysical and electrochemical properties are reported together with those of [Ru(bpy)(2)(ppb)](2+) and [Ru(bpy)(2)(mu-ppb)Ru(bpy)(2)](4+) (ppb = dipyrido[2,3a:3',2'-c]phenazine) for comparison. In all cases, the first excited state corresponds to an intramolecular TTF -> ppb charge-transfer state, Both ruthenium(II) complexes show two strong and well-separated metal-to-ligand charge-transfer (MLCT) absorption bands, whereas the (MLCT)-M-3 luminescence is strongly quenched via electron transfer from the TTF subunit. Clearly, the transient absorption spectra illustrate the role of the TTF fragment as an electron donor, which induces a triplet intraligand charge-transfer state ((ILCT)-I-3) with lifetimes of approximately 200 and 50 ns for mono- and dinuclear ruthenium(II) complexes, respectively.