Helicate-to-tetrahedron transformation of chiral lanthanide supramolecular complexes induced by ionic radii effect and linker length

Controlled formation of desired lanthanide supramolecular complexes is challenging because of the difficulties in predicting coordination geometry, as well as a labile coordination number. Herein, we explore the effect of ionic radii and linker length on supramolecular species formation. A helicate-to-tetrahedron transformation occurred between [Ln₂L1₃] and [Ln₄L1₆] (Ln = La, Sm, Eu, Gd, Tb and Lu). For six lanthanide ions, the unfavored tetrahedron [La₄L1₆] can only be observed in a concentrated mixture with the helicate [La₂L1₃] where no pure [La₄L1₆] species was isolated via crystallization. For Sm, Eu, Gd, Tb, the [Ln₄L1₆] supramolecular tetrahedron can be isolated via crystallization from diisopropyl ether. A similar result was also observed for Lu, but the tetrahedral structure was found to be relatively stable and transformed back to [Lu₂L1₃] much slower upon dissolution. No tetrahedron formation was observed with L3 giving rise to only [Ln₂L3₃] species, in which L3 contains a longer and more flexible linker compared with that of L1. Results show that the supramolecular transformation in these systems is governed by both the ionic radii as well as the ligand design. Special focus is on both [Eu₂L1₃] and [Eu₄L1₆] which form chiral entities and exhibit interesting circular polarized luminescence.