1,3-Thiazole as Suitable Antenna Ligand for Lanthanide Photolumines-cence in [LnCl_3(thz)_4]?0.5thz, Ln = Sm, Eu, Gd, Tb, Dy

摘要

The series of luminescent monomeric lanthanide thiazole complexes [LnCl_3(thz)_4]?0.5thz (Ln = Sm, Eu, Gd, Tb, Dy; thz = 1,3-thiazole) has been synthesised and characterised by powder and single-crystal X-ray diffraction, IR and photoluminescence spectroscopy, DTA/TG as well as elemental analysis. The colourless compounds exhibit photoluminescence in the visible region with varying quantum efficiencies up to QY = 48% for [TbCl_3(thz)_4]-0.5thz. Both, the lanthanide ions as well as the thiazole ligand contribute to the luminescence. Excitation can be achieved via intra-4f transitions and by exciting the ligand, emission is observed mainly from the lanthanide ions again by 4f transitions. Thiazole can transfer energy to the lanthanide ions, which further feeds the lanthanide emission by an efficient antenna effect even at room temperature. The lanthanide ions show pentagonal-bipyramidal coordination by three chloride anions and four N atoms of 1,3-thiazole, which leads to a strong ~5Do → ~7F_4 transition for europium. Significant differences arise as compared to thiophene complexes because no sulphur atom is involved in the metal coordination, as the thiazole ligand is solely coordinated via its nitrogen function.