New antenna ligand, 2-(phenylethynyl)-1,10-phenanthroline (PEP), and its luminescent Eu (III) complexes, Eu(PEP)2Cl3 and Eu(PEP)2(NO3)3, are synthesized and characterized. The synthetic procedure applied is based on reacting of europium salts with ligand in hot acetonitrile solutions in molar ratio 1 to 2. The structure of the complexes is refined by X-ray diffraction based on the single crystals obtained. The compounds [Eu(PEP)2Cl3]·2CH3CN and [Eu(PEP)2(NO3)3]∙2CH3CN crystalize in monoclinic space group P21/n and P21/c, respectively, with two acetonitrile solvent molecules. Intra- and inter-ligand π-π stacking interactions are present in solid stat and are realized between the phenanthroline moieties, as well as between the substituents and the phenanthroline units. The optical properties of the complexes are investigated in solid state, acetonitrile and dichloromethane solution. Both compounds exhibit bright red luminescence caused by the organic ligand acting as antenna for sensitization of Eu (III) emission. The newly designed complexes differ in counter ions in the inner coordination sphere, which allows exploring their influence on the stability, molecular and supramolecular structure, fluorescent properties and symmetry of the Eu (III) ion. In addition, molecular simulations are performed in order to explain the observed experimental behavior of the complexes. The discovered structure-properties relationships give insight on the role of the counter ions in the molecular design of new Eu (III) based luminescent materials.
Light-emitting phosphors, doped with lanthanide ions of Tb(III) and Sm(III) of the type Gd1.97-y SmyTb0.03(MoO4)3 (y = 0.01–0.11, step 0.02) and Gd1.95-xSm0.05Tbx(MoO4)3 (x = 0.01–0.09, step 0.02), were synthesized and characterized by X-ray diffraction, UV-Vis spectroscopy, scanning and transmitting electron microscopy (SEM, TEM) as well as photoluminescence spectroscopy. The effect of the doping content of Tb/Sm was followed. The unit cell parameters for Gd1.97-ySmyTb0.03(MoO4)3 and Gd1.95-xSm0.05Tbx(MoO4)3 changed with the increase in the Tb/Sm content. The microstrain values also increased, proposing an increased concentration of defects. The mean particle size was estimated to be approximately 0.6 µm. Based on a Williamson–Hall plot, the size of the crystallites was determined to be in the range of 42–60 nm for modified and pure Gd2(MoO4)3 samples, respectively. The samples excited at 406 nm exhibited characteristic emission lines of Sm (485, 555, 646 nm). The host material Gd2(MoO4)3 emission in visible light was explained by the crystal structure defects, namely, oxygen vacancies. The CIE x/y color coordinates of the phosphors were determined and the related points were located in the green-yellow/pale yellow region of the visible light. The excited state lifetimes were determined for both groups of the samples, showing values in the millisecond range and indicating the samples as promising phosphors.
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