Carboxylate and amidinate ligands bound to MM quadruply bonded metal centers (MM=Mo2, MoW and W2) allow for M2 δ to ligand conjugation and afford metal to ligand charge transfer absorptions that can span the region 400 - 1100 nm. The 1MLCT states have relatively long lifetimes τ1 ~ 1 to 25ps before intersystem crossing to triplet states occur τ3 ~ 10 ns, MLCT and 1 - 100 μs for delta-delta start. The application of ultra-fast fs and ns spectroscopies allows these excited states to be probed with respect to both their dynamics and charge localization. Complexes having one, two, three and four π-acceptor ligands have been studied and examples of localized and delocalized excited states have been found. The experimental results have been correlated with predictions based on electronic structure calculations based on singlet ground state and on calculations of the anion. These studies underpin the application of these systems for photon harvesting for both photocatalysis and photovoltaics. Applications to ground state photovoltaics have been made by photo-induced charge transfer to molecular and solid state inorganic oxides.<br/><i>UGC </i>

Studies of metal to ligand charge transfer states involving MM quadruply bonded complexes

249th National Meeting (2015)

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