Enhanced electrochemical and electrocatalytic activity of a new supramolecular manganese-porphyrin species containing four bis(bipyridine)(aqua)ruthenium(II) complexes

A novel supramolecular species [MnTPyP{Ru(bipy)2H2O}4](PF6)9 containing four cis-bis(bipyridine)(aqua)ruthenium(II) complexes attached to the peripheral pyridyl groups of meso-tetra(4-pyridyl)porphyrin manganese(III) (MnTPyP) has been synthesized, and employed as the precursor of a rather promising multinuclear oxo-transfer catalyst. This complex forms molecular films by dip coating. Such films are soluble in water, but can be stabilized by exchanging the PF−6 anions by [Fe(CN)6]4− or [Zn–TPPS]4−. They exhibit remarkable electrochemical and electrocatalytic activity, as demonstrated in the oxidation of nitrite ions. In this case, experimental evidence supports the involvement of electrochemically generated [ORuIV]2+ groups in the oxidation reaction, reflecting the characteristic reactivity of high-valence metal–oxo complexes.