At the molecular level, photoabsorption is described within the Born-Oppenheimer approximation by an optically-allowed vertical transition from the ground state (GS) to the Franck-Condon state (FCS), which adopts an excited electronic configuration without change in nuclear geometry. Impulsively brought out of equilibrium, the molecular system relaxes rapidly to the metastable lowest-energy excited state (LE-ES) via charge density redistribution and structural reorganization (Cotic2024). In chromophores built around transition metal (TM) ions, the LE-ES often sustains intramolecular charge transfer (CT) by delocalizing the photoexcited electron-hole pair over the ion and the coordinated ligands. Such a state displays unique photoredox capabilities, which are regulated by the dynamic evolution of the metal-ligand bonds. The molecular unit also offers momentarily two reactive loci to its surroundings. When the lifetime of the LE-ES is sufficiently long, the metastable CT chromophore can trigger elementary reactions in solution and on surfaces (Gust2008). Widespread CT chromophores are high-Z TM complexes (TMC), such as [Ru(bpy) 3 ] 2+ (Prier2013). Recent progress has delivered low-Z TMC that exhibit a LE-ES of CT character, rather than the more common metal-centered (MC) character (Liu2013). The deactivation from the high-energy excited state (HE-ES) manifold to the LE-ES then stands as the predominant loss channel inherently limiting the yields and efficiencies attainable via molecular approaches to photonversion with CT chromophores (Gust2008, Cotic2024). Overcoming this hurdle is a complex task, which is engaging increasing efforts across scientific fields (Wegner2018). A promising strategy consists in utilizing the intramolecular CT before relaxation to the LE-ES. Such hot CT chromophores have been demonstrated with high-Z (Cotic2024) and to a lesser extent, with low-Z TMC (Sinha2022, Zhang2023), for bimolecular chemical reactions and short-range CT to surfaces. However, both design and optimization remain highly challenging due to the complexities associated with the experimental and theoretical mapping of competing pathways in multidimensional energy landscapes. Elucidating the mechanisms of deactivation in benchmark systems lays a solid ground for devising innovative strategies capable of harnessing the underlying processes in rationally tailored systems.