Synthesis, crystal structure, and luminescence properties of rare-earth complexes with 2,2'-bis[(diethylcarbamoyl)-methoxy]-l,l '-biphenylene

摘要

A new amide-based ligand derived from biphenyl, 2,2'-bis[(diethylcarbamoyl)-methoxy]-1, 1'-biphenylene (L), and its complexes of rare-earth picrates were synthesized. Solid complexes of lanthanide picrates (Ln = La, Nd, Eu, Gd, Tb, and Y) with this new ligand were prepared and characterized by elemental analysis, conductivity measurements, X-ray powder diffraction, and infrared spectroscopies. The molecular structure of [Gd(pic)_3L] shows that the Gd(III) is eight-coordinate by four oxygen atoms from L and the other from one bidentate and two unidentate picrates. Furthermore, [Gd(pic)_3L] units are linked by intermolecular hydrogen bonds to generate a 2-D netlike supramolecule. Under excitation, the Eu(III) complex exhibited characteristic emissions of europium. The luminescence properties of the Eu(III) complex in solid state and in CHCl_3, acetone, acetonitrile, and DMF were investigated. The lifetime of the ~5D_0 level of Eu(III) in the complex was 0.26 ms. The quantum yield Ф of the europium picrate complex was 6.67 x 10~(-3) with quinine sulfate as reference. The lowest triplet state energy level of the ligand indicates that the triplet state energy level of the ligand matches better to the resonance level of Eu(III) than Tb(III).