New Luminescent Tetranuclear Lanthanide-Based Silsesquioxane Cage-Like Architectures.

The synthesis, structure, magnetic, and luminescence properties investigations of four new cage-like lanthanide-based silsesquioxanes (Cat)2 [(PhSiO1.5 )8 (LnO1.5 )4 (O)(NO2.5 )6 (EtOH)2 (MeCN)2 ] (where Cat+ =Et4 N+ , PPh4 P+ and Ln3+ =Eu3+ , Tb3+ and (Ph4 P)4 [(PhSiO1.5 )8 (TbO1.5 )4 (O)2 (NO2.5 )8 ]⋅10MeCN are reported. They present an unusual prism-like topology of cage architectures and lanthanide-characteristic emission, which makes them the first luminescent cage-like lanthanide silsesquioxanes. One of the Tb3+ -based cages presents a magnetic spin-flip transition.