Two　pairs　of　cyanidometal-bridged　trinuclear　complexes　trans-[Cp*(modppe)Ru(μ-NC)Ru(L)4(μ-CN)Ru(modppe)Cp*][PF6]n　(n　=　2,　3;　L　=　pyridine　(py),　1[PF6]n;　4-methoxypyridine　(mopy),　2[PF6]n;　Cp*　=　1,2,3,4,5-pentamethylcyclopentadiene)　in　two　distinct　states　have　been　synthesized　and　fully　characterized.　The　investigated　results　suggest　that　1[PF6]3　and　2[PF6]3　are　Class　II　mixed　valence　complexes.　The　IR　spectroscopy　and　UV–vis-NIR　spectroscopy　analyses　showed　that　with　the　increase　of　the　electron-donating　ability　of　the　auxiliary　ligand　of　the　cyanidometal　bridge,　the　degree　of　delocalization　increases　and　the　energy　of　the　metal-to-metal　charge　transfer　(MMCT)　of　the　mixed　valence　complexes　decreases,　supported　by　TDDFT　calculations.　©　2023　Elsevier　Ltd