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) A, b = 27.6044(6) A, с = 21.8615(5) A, β = 105.172(1)°, V = 7116.9(3) A3, Z = 4) and Dy(dpm)3 (2) at 200(2) K (space group Pmn21, a = 17.8741(7) A, b = 10.5639(4) A, с = 9.8336(4) A, V = 1856.78(13) A3, 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.