Crystal Structures of [Dy(dpm)3]2 and Dy(dpm)3, Luminescent and X-Ray Fluorescent Study of Lanthanide(III) Tris-Dipivaloylmethanates

Abstract

Crystal structures of [Dy(dpm)₃]₂ (1) at 155(2) K (space group P2₁/n, a = 12.2191(3) Å, b = 27.6044(6) Å, с = 21.8615(5) Å, β = 105.172(1)°, V = 7116.9(3) ų, Z = 4) and Dy(dpm)₃ (2) at 200(2) K (space group Pmn2₁, a = 17.8741(7) Å, b = 10.5639(4) Å, с = 9.8336(4) Å, V = 1856.78(13) ų, Z = 2) are determined. The structure of complex 1 is similar to the previously known dimeric packings [Ln(dpm)₃]₂ (Ln = La, Pr, Nd, Eu, Gd, Tb). Complex 2 is isostructural to the previously studied molecular complexes Er(dpm)₃ and Lu(dpm)₃. At room temperature the luminescence quantum yield (QY) of Tb(dpm)₃ is found to reach 77% and that of Dy(dpm)₃ is 5%, while for the other Lu(dpm)₃ complexes, where Ln = Pr, Nd, Sm, Eu, Gd, Ho, Er, Tm, Yb, QY is below 1%. A series of [Tb(dpm)₃]₂ and Dy(dpm)₃ solid solutions is obtained by evaporating mixtures from solutions. Molecular films of these complexes on Si, Cu, Ni, Ti, KBr substrates are obtained by vacuum deposition.