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)(LnO(1.5))(4)(O)(NO2.5)(6)(EtOH)(2)(MeCN)(2)] (where Cat(+)=Et4N+, PPh(4)P(+)and Ln(3+)=Eu3+, Tb(3+)and (Ph4P)(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.