Guest-Driven Self-Assembly and Chiral Induction of Photofunctional Lanthanide Tetrahedral Cages

Chiral luminescent lanthanide-organic cages have many potential applications in enantioselective recognition, sensing, and asymmetric catalysis. However, due to the paucity of structures and their limited cavities, host-guest chemistry with lanthanide-organic cages has remained elusive so far. Herein, we report a guest-driven self-assembly and chiral induction approach for the construction of otherwise inaccessible Ln₄L₄-type (Ln = lanthanide ions, i.e., Eu^III, Tb^III; L = ligand) tetrahedral hosts. Single crystal analyses on a series of host-guest complexes reveal remarkable guest-adaptive cavity breathing on the tetrahedral cages, reflecting the advantage of the variation tolerance on coordination geometry of the f-elements. Meanwhile, noncovalent confinement of pyrene within the lanthanide cage not only leads to diminishment of its excimer emission but also facilitates guest to host energy transfer, opening up a new sensitization window for the lanthanide luminescence on the cage. Moreover, stereoselective self-assembly of either Λ₄- or Δ₄- type Eu₄L₄ cages has been realized via chiral induction with R/S-BINOL or R/S-SPOL templates, as confirmed by NMR, circular dichroism (CD), and circularly polarized luminescence (CPL) with high dissymmetry factors (g_lum) up to ±0.125.