Six complexes consisting of either 2,6-bis(1H-benzimidazol-2-yl)pyridine (bbp) or 2,2′:6′,2″-terpyridine (tpy) moieties coordinated to ruthenium(II) and attached to (pentaphenoxy)cyclotriphosphazene were synthesised and structurally characterised by single-crystal X-ray diffraction techniques. Two of the complexes are the first examples of structurally characterised mono-protonated Ru(bbp)(tpy) complexes. The new complexes were studied by NMR, electronic absorption and vibration spectroscopy to gain an understanding of their physical characteristics. Remarkably the mono-deprotonated form of the bbp ligand, but only when attached to (pentaphenoxy)cyclotriphosphazene by a pyridyl phosphoester linker, shows an equivalence of the benzimidazole/benzimidazolate moieties on the NMR time scale, but not on the electronic time scale, as evidenced by UV–Vis and resonance Raman spectroscopy.