Visible Circularly Polarized Luminescence of Octanuclear Circular Eu(III) Helicate

This work reports on the structural and photophysical characterization of D₄-symmetrical octanuclear circular Ln^III helicates, [(R)- or (S)-ⁱPr-Pybox]₈(Ln^III)₈(THP)₈ (where Ln = Eu and Tb, THP = trianionic tris-β-diketonate, and ⁱPr-Pybox = chiral bis(4-isopropyl-2-oxazolinyl)pyridine). X-ray crystallographic analysis revealed that the octanuclear circular helicate possesses square antiprism architecture and consists of four [(R)- or (S)-ⁱPr-Pybox]₂Ln^III₂(THP)₂ asymmetric units arranged in a closed ring form. Ligand-to-ligand interactions between the THP and the ⁱPr-Pybox ligands have successfully directed formation of enantiopure, homoconfigurational (Δ,Δ,Δ,Δ,Δ,Δ,Δ,Δ)-R and (Λ,Λ,Λ,Λ,Λ,Λ,Λ,Λ)-S isomers. All of the nonacoordinated Ln^III ions are identical and exhibit a distorted capped square antiprism (CSAP) geometry. Upon excitation of the ligand absorption band (λ = 360 nm), the circular helicates display characteristic Eu^III (red, ⁵D₀ → ⁷F_J, J = 0-4) or Tb^III (green, ⁵D₄ → ⁷F, J = 6-3) core f-f luminescence. The overall emission quantum yields of the circular Eu^III and Tb^III helicates are 0.145 and 0.0013, respectively, in chloroform. The Eu^III and Tb^III complexes exhibit remarkable circularly polarized luminescence (CPL) activity at their magnetic dipole transition with observed luminescence dissymmetry factors |g_lum| of 1.25 (⁵D₀ → ⁷F₁, λ = 592 nm) and 0.25 (⁵D₄ → ⁷F_5, λ = 541 nm), respectively. Exceptional |g_lum| values of the circular Eu^III helicates highlight the visible intensity difference between left and right circularly polarized emissions of R and S isomers in chloroform and PMMA thin film.