Conglomerate, Racemate, and Achiral Crystals of Polymetallic Europium(III) Compounds of Bis- or Tris-β-diketonate Ligands and Circularly Polarized Luminescence Study

[Image: see text] This work reports (a) conglomerate and racemic crystal structures of [(Δ,Δ,Δ,Δ,Δ,Δ)- or/and (Λ,Λ,Λ,Λ,Λ,Λ)-Eu(III)(6)(TTP)(8)(OH(2))(6)Na(4)](n) coordination polymers, (b) racemic crystal structures of (Δ,Δ,Δ,Δ)-/(Λ,Λ,Λ,Λ)-Eu(III)(4)(TTP)(4)(bipy)(4)(MEK)(2)(OH(2))(2) tetrahedral clusters, and (c) the achiral crystal structure of the [Eu(III)(2)(BTP)(4)(OH(2))(2)Na(2)](n) coordination polymer (where BTP = dianionic bis-β-diketonate, TTP = trianionic tris-β-diketonate, and bipy = 2,2′-bipyridine). The screw coordination arrangement of the TTP ligand has led to the formation of homoconfigurational racemic Eu(III) products. The conglomerate crystallization of [Eu(III)(6)(TTP)(8)(OH(2))(6)Na(4)](n) appears to be caused by the presence of the sodium, Na(+) counterions, and interactions between oxygen atoms and the trifluoromethyl unit of the TTP ligand and Na(+) ions. All the Eu(III) compounds exhibit characteristic red luminescence ((5)D(0) → (7)F(J), J = 0–4) in solution or in the solid crystalline state. Circularly polarized luminescence (CPL) was observed in the chiral Eu(III)(6)(TTP)(8)(OH(2))(6)Na(4)](n) species, displaying a |g(lum)| value in the range of 0.15 to 0.68 at the (5)D(0) → (7)F(1) emission band. Subtle changes of the [Eu(III)(6)(TTP)(8)(OH(2))(6)Na(4)](n) structure which may be due to selection of twinned crystals or crystals that do not correspond to a perfect spontaneous resolution, are considered to be responsible for the variation in the observed CPL values.