Photophysical Characterizationand Excited State Dynamicsof Decamethylruthenocenium

Understanding the landscape of molecular photocatalysis is vital to enable efficient conversion of feedstock molecules to targeted products and inhibit off-cycle reactivity. In this study, the light-promoted reactivity of [RuCp*₂]⁺ was explored via electronic structure, photophysical, and photostability studies and the reactivity of [RuCp*₂]⁺ within a photocatalytic hydrogen evolution cycle was assessed. TD-DFT calculations support the assignment of a low-energy ligand-to-metal charge transfer transition (LMCT) centered at 500 nm, where an electron from a ligand-based orbital delocalized across both Cp* ligands is promoted to a d_{<i>x</i>²–<i>y</i>²}-based β-LUMO orbital. Upon irradiating the LMCT absorption feature, ultrafast transient absorption spectroscopy measurements show that an initial excited state (τ₁ = 1.3 ± 0.1 ps) is populated, which undergoes fast relaxation to a longer-lived state (τ₂ = 12.0 ± 0.9 ps), either via internal conversion or vibrational relaxation. Despite the short-lived nature of these excited states, bulk photolysis of [RuCp*₂]⁺ demonstrates that photochemical conversion to decomposition products is possible upon prolonged illumination. Collectively, these studies reveal that [RuCp*₂]⁺ undergoes light-driven decomposition, highlighting the necessity to construct molecular photocatalytic systems resistant to off-cycle reactivity in both the ground and excited states.