Electrogenerated chemiluminescence properties of bisalicylideneethylenediamino (salen) metal complexes

The spectroscopy, electrochemistry and electrogenerated chemiluminescence (ECL) of eight bisalicylideneethylenediamino (salen) metal complexes are reported. Two of the complexes contain an unsubstituted salen ligand and either cobalt(II) or nickel(II). The others have 1,2-cyclohexanediamonio-N,N′-bis(3,5-di-t-butylsalicylidene) as the ligand, and chromium(III), aluminum(III), cobalt(II), cobalt(III) or manganese(II) as the metal center. The complexes have lowest energy absorption maxima between 350 and 430 nm. When excited at these wavelengths, the complexes emit between 417 and 594 nm in acetonitrile. Photoluminescence efficiencies (ϕem) were between 0.0310 and 23.8 compared to Ru(bpy)32+ (bpy = 2,2′-bipyridine; ϕem = 1), with the aluminum complexes displaying the most intense photoluminescence. Both reversible and irreversible oxidative electrochemistry is displayed by the metal–salen complexes with oxidation potentials ranging between +0.152 and +1.661 V versus Ag/AgCl. The ECL intensity peaks at a potential corresponding to oxidation of both TPrA and the salen systems, indicating that both are involved in the ECL reaction sequence. ECL efficiencies (ϕecl) were between 0.0018 and 0.0086 when compared to Ru(bpy)32+ (ϕecl = 1) in acetonitrile (0.05 M tri-n-propylamine (TPrA) as an oxidative–reductive ECL coreactant). Also, qualitative studies using transmission filters suggest that the complexes emit ECL in approximately the same region as their photoluminescence, indicating that the same excited state is formed in both experiments.

The spectroscopy, electrochemistry and coreactant electrogenerated chemiluminescence (ECL) properties of eight bisalicylideneethylenediamino (salen) metal complexes are reported.Figure optionsDownload as PowerPoint slideHighlights
► Metal–salen complexes display coreactant electrogenerated chemiluminescence in acetonitrile.
► Photoluminescent efficiencies are often higher than a Ru(bpy)32+ standard, while ECL efficiencies are lower.
► The excited states and redox potentials of the complexes are sensitive to the metal center.