A02 - Photo-PCET Mediators for Selective Bond Activation and Formation

Project A02 will study light-induced (multiple) excited state PCET (ES-PCET) in solution to develop ES-PCET mediators for challenging chemical transformations. Two classes of photoactive ES-PCET mediators will be addressed as archetypal species for reductive and oxidative catalysis:
Non-noble metal-functionalized molecular polyoxometalate clusters (POMs) will be developed, which undergo ES-PCET from ligand-to-metal charge-transfer (LMCT) excited states. The project aims at addressing the fundamental photophysics and -chemistry, in particular, with respect to supramolecular effects (pre-aggregation, ion interactions). The photo-active POMs also provide molecular models for the (doped) ZnO (photo)PCET materials examined in the C group.
Low-valent photoactive transition metal hydride complexes (TMHs) that undergo ES-PCET from metal-to-ligand charge-transfer (MLCT) excited states will be examined. The project aims at deriving the mechanisms of hydride photo-PCET and develop predictive models for the driving-force dependence.