Computational details: Hot-carrier injection and millisecond charge separation from a robust heteroleptic iron(II) chromophore immobilized on TiO2

Computational details: The fully relaxed equilibrium structures of Fe(Cpy)2(deeb) (in acetonitrile) were obtained considering three electronic scenarios, namely the (closed-shell or low-spin) singlet ground state (S0) as well as two triplet species, i.e. triplet (open-shell) high-spin species in particular the triplet and quintet ground states, i.e., triplet metal-centered (3MC) and triplet metal-to-ligand-charge transfer (3MLCT) states, respectively. The full dataset was obtained based on the B3LYP10, TPSSh and B3LYP functionals (with increasing amount of exact exchange). For each subfolder – for each species – contains the respective xyz-structure, high resolution images of charge density difference plots (CDDs) and, in case of open-shell species also the spin density. Furthermore, cub-files are provided accordingly. Furthermore, doubly deprotonated Fe(Cpy)2(dcb) was immobilized by both carboxylate anchoring groups onto an anatase (101) surface, modeled using the atomic simulation environment. A [Ti52O102]4+ cluster was constructed with a Fe(Cpy)2(dcb) complex – anchored by both anchoring groups. The structure was partially relaxed at the xTB0 level of theory in gas phase within singlet as well as triplet configurations. The anatase cluster was kept frozen except for the two Ti atoms connected to the carboxylate groups.