Electron transfer properties of singlet oxygen and promoting effects of scandium ion

Electron-transfer kinetics from strong one-electron reductants such as decamethylferrocene and chromium-(II) complexes to singlet oxygen (¹O₂: ¹Δ_g) were examined using laser flash photolysis in oxygen-saturated deuterated acetonitrile. The formation of decamethylferricenium ion in electron transfer from decamethylferrocene to ¹O₂ was observed as a transient absorption band at λ_max = 780 nm, whereas the formation of O₂^.- is detected as a transient absorption spectrum of hexyl viologen radical cation (λ_max = 600 nm) which is formed by an electron transfer from O₂^.- to hexyl viologen. The reorganization energy of the electron-transfer reduction of ¹O₂ in acetonitrile has been determined as 1.73 ± 0.14 eV from the analysis of the rate constants of electron transfer from the one-electron reductants to ¹O₂ in light of the Marcus theory of electron transfer. The solvent-dependent reorganization energy of ¹O₂ in acetonitrile is smaller than the corresponding value of ground-state oxygen in water (1.97 ± 0.03 eV), reflecting the longer O-O bond length in the excited state in reference to the ground state and the smaller solvation in acetonitrile. The reactivity of ¹O₂ in an outer-sphere electron-transfer reaction from ferrocene to ¹O₂ is enhanced by the addition of scandium triflate [Sc(OTf)₃]. This is ascribed to the strong binding of Sc³⁺ with the one-electron reduced species, i.e., O₂^.- rather than the excited state (¹O₂).