Highly Stable Europium(III) Tetrahedral (Eu₄L₄)(phen)₄ Cage: Structure, Luminescence Properties, and Cellular Imaging

Luminescent lanthanide cages have many potential applications in guest recognition, sensing, magnetic resonance imaging (MRI), and bioimaging. However, these polynuclear lanthanide assemblies' poor stability, dispersity, and luminescence properties have significantly constrained their practical applications. Furthermore, it is still a huge challenge to simultaneously synthesize and design lanthanide organic polyhedra with high stability and quantum yield. Herein, we demonstrate a simple and robust strategy to improve the rigidity, chemical stability, and luminescence of an Eu(III) tetrahedral cage by introducing the conjugated planar auxiliary phen ligand. The self-assembled tetrahedral cage, (Eu₄L₄)(phen)₄ [L = (4,4',4″-tris(4,4,4-trifluoro-1,3-dioxobutyl)-triphenylamine), phen = 1,10-phenanthroline], exhibited characteristic luminescence of Eu³⁺ ions with high quantum yield (41%) and long lifetime (131 μs) in toluene (1.0 × 10^-6 M). Moreover, the Eu(III) cage was stable in water and even in an aqueous solution with a pH range of 1-14. 3-(4,5-Dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay and cellular imaging revealed that the Pluronic F127-coated hybrid material, (Eu₄L₄)(phen)₄@F127, exhibited low cytotoxicity, good biocompatibility, and cellular imaging ability, which may inspire more insights into the development of lanthanide organic polyhedra (LOPs) for potential biomedical applications.