Triply halogeno and methoxido-bridged dinuclear ruthenium complexes bearing a tridentate ancillary ligand, alkylbis(2-pyridylmethyl)amine (alkyl, ethyl and benzyl), in the Ru(II)–Ru(III) mixed-valence state were synthesized by reduction reactions of the trichloridoruthenium(III) complex, fac-[RuIIICl3(ebpma)], followed by chlorido-substitution and oxidation reactions in air. The conversion of the bridging ligands of the diruthenium complexes was also made possible through reduction of the dinuclear core. The electronic structures of the mixed-valence state were investigated by electron spin resonance (ESR), X-ray crystallography, electrochemical measurements and UV-vis-near infrared (NIR) spectroscopy. The mixed-valence state of all the triply bridged complexes was stable and classified as Class III.
