Properties of Amine-Containing Ligands That Are Necessary for Visible-Light-Promoted Catalysis with Divalent Europium

We describe a study of the influence of amine-containing ligands on the photoredox-relevant properties of Eu^II toward the rational design of Eu^II-containing catalysts for visible-light-promoted photoredox reactions. We report our observations of the effects of the degree of functionalization of amines, denticity, and macrocylic ligands on the absorbance of Eu^II. Ligands that contain secondary amines bathochromically shift the absorbance of EuCl₂ relative to ligands that contain primary or tertiary amines. Similarly, ligands of larger denticity have a larger bathochromic shift of the absorbance than ligands of smaller denticity. We observed that macrocyclic ligands have a larger effect on the absorbance of EuCl₂ than nonmacrocyclic ligands. Also, we report the photoredox reactivity of four new Eu^II-containing complexes. These observations are potentially influential in understanding the ligand properties that promote the use of Eu^II in visible-light-promoted photoredox catalysis.