Enhanced Electron-Transfer Reactivity of a Long-Lived Photoexcited State of a Cobalt-Oxygen Complex

Photodynamics and electron-transfer reactivity of an excited state derived from an earth-abundant mononuclear cobalt-oxygen complex ground state, [(TAML)Co^IV(O)]^2- (1; H₄TAML = 3,4,8,9-tetrahydro-3,3,6,6,9,9-hexamethyl-1 H-1,4,8,11-benzotetraazo-cyclotridecane-2,5,7,10-(6 H, 11 H)tetrone), prepared by electron-transfer oxidation of Li[(TAML)Co^III]·3(H₂O) (2) in a 1:1 acetonitrile/acetone solvent mixture at 5 °C, were investigated using a combination of femtosecond and nanosecond laser absorption spectroscopy. Visible light photoexcitation of 1 (λ_exc = 393 nm) resulted in generation of the excited state S₂* (lifetime: 1.4(4) ps), detected 2 ps after laser irradiation by femtosecond laser spectroscopy. The initially formed excited state S₂* converted to a lower-lying excited state, S₁* (λ_max = 580 nm), with rate constant k_c = 7(2) × 10¹¹ s^-1 (S₂* → S₁*). S₁* exhibited a 0.6(1) ns lifetime and converted to the initial ground state 1 with rate constant k_d = 1.7(3) × 10⁹ s^-1 (S₁* → 1). The same excited state dynamics was observed when 1 was generated by electron-transfer oxidation of 2 using different one-electron oxidants such as Cu(OTf)₂ (OTf^- = triflate anion), [Fe(bpy)₃]³⁺ (bpy = 2,2'-bipyridine), and tris(4-bromophenyl)ammoniumyl radical cation (TBPA^•+). The electron-transfer reactivity of S₁* was probed by nanosecond laser photoexcitation of 1 in the presence of a series of electron donors with different one-electron oxidation potentials ( E_ox vs SCE): benzene (2.35 V), toluene (2.20 V), m-xylene (2.02 V), and anisole (1.67 V). The excited state S₁* engaged in electron-transfer reactions with m-xylene and anisole to generate π-dimer radical cations of m-xylene and anisole, respectively, observed by nanosecond laser transient absorption spectroscopy, whereas no reactivity was observed toward benzene and toluene. Such differential electron-transfer reactivity depending on the E_ox values of electron donors allowed the estimation of the one-electron reduction potential of S₁* ( E_red*) as 2.1(1) V vs SCE, which is much higher than that of the ground state ( E_red = 0.86 V vs SCE).