A Highly Luminescent Chiral Tetrahedral Eu₄L₄(L′)₄ Cage: Chirality Induction, Chirality Memory, and Circularly Polarized Luminescence

Abstract

Chiral lanthanide cages with circularly polarized luminescence (CPL) properties have found potential application in enantioselective guest recognition and sensing. However, it still remains a big challenge to develop a simple and robust method for the diastereoselective assembly of homochiral lanthanide cages in view of the large lability of the Ln(III) ions. Herein, we report the first example of the formation of a enantiopure lanthanide tetrahedral cage via a chiral ancillary ligand induction strategy. One such cage, (Eu4L4)(R/S-BINAPO)4, is assembled by four achiral C3-symmeric tris(β-diketones) (4,4′,4″-tris(4,4,4-trifluoro-1,3-dioxobutyl)triphenylamine, L) as faces, four Eu(III) ions as vertices and four chiral R-/S-bis(diphenylphosphoryl)-1,1′-binaphthyl (R/S-BINAPO) as ancillary ligands. X-ray crystallography and NMR and CD spectra confirm the formation of a pair of enantiopure chiral topological tetrahedral cages, (Eu4L4)(R-BINAPO)4 and (Eu4L4)(S-BINAPO)4 (ΔΔΔΔ-1 and ΛΛΛΛ-1). As expected, the tetrahedral cages present strong CPL with |glum| values up to 0.20, while they unexpectedly give ultrahigh luminescent quantum yields (QYs) of up to 81%, the highest value reported in chiral Ln(III) complexes. More impressively, the chiral memory effect for a lanthanide-based assembly is observed for the first time. The chirality of the original cage 1 framework is retained after R/S-BINAPO is replaced by the achiral bis[2-(diphenylphosphino)phenyl] ether oxide (DPEPO), and thus another pair of enantiopure Eu(III) tetrahedral cages, ΔΔΔΔ- and ΛΛΛΛ-[(Eu4L4)(DPEPO)4] (ΔΔΔΔ-2 and ΛΛΛΛ-2), have been isolated. Encouragingly, cage 2 also presents an impressive luminescence quantum yield (QY = 68%) and intense CPL (|glum| = 0.11). This study offers a simple and low-cost synthesis strategy for the preparation of lanthanide cages with CPL properties.