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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 dx2–y2-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. 

The ligand-to-metal charge transfer (LMCT) transitions of [Re(dmpe)3]2+ (dmpe = bis-1,2-(dimethylphosphino)ethane) were interrogated using UV/Vis absorbance spectroscopy, photoluminescence spectroscopy, and time-dependent density functional theory. The solvent dependence of the lowest energy charge transfer transition was quantified; no solvatochromism was observed. TD-DFT calculations reveal the dominant LMCT transition is highly symmetric and delocalized involving all phopshine ligand donors in the charge transfer, providing an understanding for the absence of solvatochromism of [Re(dmpe)3]2+.