Intermediate Valence States in Lanthanide Compounds

Over more than 50 years, intermediate valence states in lanthanide compounds have often resulted in unexpected or puzzling spectroscopic and magnetic properties. Such experimental singularities could not be rationalised until new theoretical models involving multiconfigurational electronic ground states were established. In this minireview, the different singularities that have been observed among lanthanide complexes are highlighted, the models used to rationalise them are detailed and how such electronic effects may be adjusted depending on energy and symmetry considerations is considered. Understanding and tuning the ground‐state multiconfigurational behaviour in lanthanide complexes may open new doors to modular and unusual reactivities.