Ligand-to-Ligand Interactions That Direct Formation of D₂-Symmetrical Alternating Circular Helicate

This work demonstrates that ligand-to-ligand interactions between achiral bis-β-diketonate (BTP) and chiral bis(4-phenyl-2-oxazolinyl)pyridine [( R)- or ( S)-Ph-Pybox] are successfully directed to the fabrication of a D₂-symmetrical alternating circular helicate with the general formula [( R)- or ( S)-Ph-Pybox]₄(Ln^III)₄(BTP)₆. The lanthanide(III) Ln^III assemblies (Ln^III₄- RRRR and Ln^III₄- SSSS) have a nanometer-size squarelike grid (interatomic distances > 10 Å). X-ray structure analysis revealed that the circular helicate contains two double helicate Ln^III₂L₂ units, where both show ( M)-helicity for Ln^III₄- RRRR and ( P)-helicity for Ln^III₄- SSSS, where π-π stacking interaction is present between the side arm of ( R)-Ph-Pybox (Ph₁) and the adjacent BTP ligand around the Eu^III metal center ( d_ππ = 3.636 Å: the diketonate plane···Ph₁ distance). The newly obtained circular lanthanide(III) helicate exists as single and homochiral diastereomers in solution (Ln^III₄- RRRR and Ln^III₄- SSSS), exhibiting circularly dichroism (CD) and circularly polarized luminescence (CPL). Conversely, the circular helicate favors the heterochiral arrangement (i.e., Ln^III₄- RRRR/Ln^III₄- SSSS).