ABSTRACT
Y3Al5O12:Ce3+ (YAG:Ce) nanoparticles were prepared by a two-step approach including ionic-liquid-assisted particle formation and LiCl-matrix-treated crystallization. Subsequent to particle formation in [MeBu3N][N(SO2CF3)2] as the ionic liquid (MeBu3N: tributylmethylammonium; N(SO2CF3)2: bis(trifluoromethanesulfonyl)imide), the as-obtained amorphous precursor nanoparticles were crystallized in a LiCl matrix (600 °C, 1 h). The resulting YAG:Ce nanoparticles are well crystallized and exhibit a diameter of about 40 nm. They show bulk-like luminescence and a quantum yield of 51(±3)%. The selected Y : Al ratio and temperature profile turned out to be optimal for the synthesis strategy in terms of particle size and luminescence properties although minor amounts of CeO2 remained. The YAG:Ce nanoparticles can be easily redispersed in the liquid phase and embedded in polymers such as polyester. The course of the reaction and the properties of the nanoparticles are characterized by electron microscopy, dynamic light scattering, infrared spectroscopy, X-ray powder diffraction, and fluorescence spectroscopy.
ABSTRACT
The reaction of manganese(ii) bromide and the crown ether 18-crown-6 in the ionic liquid [(n-Bu)3MeN][N(Tf)2] under mild conditions (80-130 °C) resulted in the formation of three different coordination compounds: MnBr2(18-crown-6) (), Mn3Br6(18-crown-6)2 () and Mn3Br6(18-crown-6) (). In general, the local coordination and the crystal structure of all compounds are driven by the mismatch between the small radius of the Mn(2+) cation (83 pm) and the ring opening of 18-crown-6 as a chelating ligand (about 300 pm). This improper situation leads to different types of coordination and bonding. MnBr2(18-crown-6) represents a molecular compound with Mn(2+) coordinated by two bromine atoms and only five oxygen atoms of 18-crown-6. Mn3Br6(18-crown-6)2 falls into a [MnBr(18-crown-6)](+) cation - with Mn(2+) coordinated by six oxygen atoms and Br - and a [MnBr(18-crown-6)MnBr4](-) anion. In this anion, Mn(2+) is coordinated by five oxygen atoms of the crown ether as well as by two bromine atoms, one of them bridging to an isolated (MnBr4) tetrahedron. Mn3Br6(18-crown-6), finally, forms an infinite, non-charged [Mn2(18-crown-6)(MnBr6)] chain. Herein, 18-crown-6 is exocyclically coordinated by two Mn(2+) cations. All compounds show intense luminescence in the yellow to red spectral range and exhibit remarkable quantum yields of 70% (Mn3Br6(18-crown-6)) and 98% (Mn3Br6(18-crown-6)2). The excellent quantum yield of Mn3Br6(18-crown-6)2 and its differentiation from MnBr2(18-crown-6) and Mn3Br6(18-crown-6) can be directly correlated to the local coordination.
ABSTRACT
Eu3+-modified carbon dots (C-dots), 3-5 nm in diameter, were prepared, functionalized, and stabilized via a one-pot polyol synthesis. The role of Eu2+/Eu3+, the influence of O2 (oxidation) and H2O (hydrolysis), as well as the impact of the heating procedure (conventional resistance heating and microwave (MW) heating) were explored. With the reducing conditions of the polyol at the elevated temperature of synthesis (200-230 °C), first of all, Eu2+ was obtained resulting in the blue emission of the C-dots. Subsequent to O2-driven oxidation, Eu3+-modified, red-emitting C-dots were realized. However, the Eu3+ emission is rapidly quenched by water for C-dots prepared via conventional resistance heating. In contrast to the hydroxyl functionalization of conventionally-heated C-dots, MW-heating results in a carboxylate functionalization of the C-dots. Carboxylate-coordinated Eu3+, however, turned out as highly stable even in water. Based on this fundamental understanding of synthesis and material, in sum, a one-pot polyol approach is established that results in H2O-dispersable C-dots with intense red Eu3+-line-type emission.
ABSTRACT
C-dots (3-5 nm in diameter) obtained by most simple heating of polyols (glycerol, diethylene glycol and PEG 400) show intense blue and green emission (50% quantum yield). Upon modification with TbCl3/EuCl3, energy transfer from the C-dots to the rare-earth metal results in line-type Tb(3+) (green)/Eu(3+) (red) emission with quantum yields up to 85%.
Subject(s)
Europium/chemistry , Luminescent Agents/chemistry , Nanotubes, Carbon/chemistry , Polymers/chemical synthesis , Terbium/chemistryABSTRACT
A series of 12 dinuclear complexes [Ln2Cl6(µ-4,4'-bipy)(py)6], Ln=Y, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, (1-12, respectively) was synthesized by an anhydrous solvothermal reaction in pyridine. The complexes contain a 4,4'-bipyridine bridge and exhibit a coordination sphere closely related to luminescent lanthanide MOFs based on LnCl3 and 4,4-bipyridine. The dinuclear complexes therefore function as a molecular model system to provide a better understanding of the luminescence mechanisms in the Ln-N-MOFs (∞)(2)[Ln2Cl6(4,4'-bipy)3]·2(4,4'-bipy). Accordingly, the luminescence properties of the complexes with Ln=Y, Sm, Eu, Gd, Tb, Dy, (1, 4-8) were determined, showing an antenna effect through a ligand-metal energy transfer. The highest efficiency of luminescence is observed for the terbium-based compound 7 displaying a high quantum yield (QY of 86%). Excitation with UV light reveals typical emission colors of lanthanide-dependent intra 4f-4f-transition emissions in the visible range (Tb(III) : green, Eu(III) : red, Sm(III) : salmon red, Dy(III) : yellow). For the Gd(III)- and Y(III)-containing compounds 6 and 1, blue emission based on triplet phosphorescence is observed. Furthermore, ligand-to-metal charge-transfer (LMCT) states, based on the interaction of Cl(-) with Eu(III), were observed for the Eu(III) compound 5 including energy-transfer processes to the Eu(III) ion. Altogether, the model complexes give further insights into the luminescence of the related MOFs, for example, rationalization of Ln-independent quantum yields in the related MOFs.
