Photoluminescence of Homoleptic Lanthanide Complexes With Tris(benzotriazol-1-yl)borate

Bright photoluminescent neutral complexes having general formula [Ln(tbtz)3] (Ln = Eu, Tb; tbtz = tris(benzotriazol-1-yl)borate) were obtained by reacting K[tbtz] with EuCl3 and TbCl3. The emissions in the visible range, related to the f-f transitions of the trivalent lanthanide ions, are observable upon excitation with wavelengths shorter than 350 nm. The most intense emission bands correspond to the 5D0 → 7F4 transition at 699 nm for the europium complex and to the 5D4 → 7F5 transition at 542 nm for the terbium derivative. The luminescence is in all the cases mostly associated with the antenna-effect from the coordinated tbtz ligands. The synthetic approach was successfully extended to the preparation of the analogous yttrium and gadolinium derivatives. Tricapped trigonal prismatic geometry was attributed to the complexes on the basis of luminescence data and DFT calculations. Highly photoluminescent plastic materials were obtained by embedding small amounts of [Eu(tbtz)3] or [Tb(tbtz)3] in poly(methyl methacrylate).