MWO4 host matrices (M: Sr, Ba) doped with different Tm3+ concentrations (0.02, 0.04, 0.06, 0.08 and 0.10 mol%) have been successfully prepared by the coprecipitation method at room temperature. The as-prepared nanophosphors were characterized by infrared spectroscopy showing intense absorption bands in the range of 700-1000 cm-1 attributed to the symmetrical and asymmetrical stretching vibrations (ν) of the tetrahedral [WO4]2- group. The X-ray diffraction (XRD) measurements reveal the tetragonal scheelite phase with the I41/a (No. 88) space group. The emission spectra of the MWO4:Tm3+ materials are dominated by the highest intensity narrow band of the intraconfigurational 1D2 → 3F4 transitions in the blue region (ca. 456 nm) arising from the Tm3+ ions. Additional low-intensity emission bands originated from the 1G4 → 3H6 (ca. 475 nm), 1G4 → 3F4 (660 nm) and 3H4 → 3H6 (700 nm) transitions are also observed. These optical results indicate that the materials can be used as an alternative to blue-emitting markers.

The [Zn3(BTC)2·12H2O] (BTC = 1,3,5-tricarboxylate) metal-organic framework (MOF) was successfully synthesized using a microwave-assisted hydrothermal synthesis technique, which allowed for significantly decreased reaction time compared to the production of the same compound via conventional heating. In situ doping with Eu3+ ions at concentrations ranging from 1.0 to 5.0 mol% produced doped materials whose emission ranged from blue to red color. The Eu3+ spectroscopic properties were used to study the incorporation of the dopant into the structure of [Zn3(BTC)2·12H2O], even at very low concentrations. These experiments confirmed the usefulness of this ion as a luminescent probe, as it permitted the identification of small variations in structure not perceptible by X-ray diffraction. The variation in the coordination environment induced by increases in doping percentage was analyzed by evaluating changes in the characteristic Eu3+ excitation and emission profiles, using them to calculate luminescence lifetimes, experimental intensity parameters Ωλ (λ: 2 and 4) as well as the intrinsic quantum yield (QEu+3Eu+3) of the 5D0 emitting level of each doped MOF. The excitation and luminescence spectra show that intramolecular energy transfer from the BTC linker to Eu3+ ion, and we could observe the emission color tuning originated from the emissions of the BTC ligand and Eu3+ ion.

In this study, a novel type of tris(2-acyl-1,3-indandione)-aluminum(III) coordination compounds of the general formula [Al(acind)3]H2O, where 2-acyl-1,3-indandione (acind), 2-acetyl-1,3-indandione (aind), 2-benzoyl-1,3-indandione (bind), and 4-methyl-2-benzoyl-1,3-indandione (mbind), were synthesized and characterized by elemental analysis (CHN), Fourier transform infrared (FTIR) and nuclear magnetic resonance (1H NMR) spectroscopies, thermal analysis (TG/DTG and DTA), and optical absorption spectroscopy in the UV-Vis region. These compounds present remarkably high green luminescence in powder and in thin-film forms. However, when these compounds are applied in glass/ITO/β-NPB/spiro-2CBP/[Al(acind)3]/Al and glass/ITO/β-NPB/[Al(acind)3]/LiF/Al electroluminescent devices, where spiro-2CBP is 2,7-bis(carbazol-9-yl)-9,9-spirobifluorene and β-NPB is N,N’-bis(naphthalen-2-yl)-N,N’-bis(phenyl)-benzidine, the emission color tuned from green to red, reflecting a change from the direct charge recombination in the emitting layer of the [Al(acind)3] complexes to an exciplex-based emission in which [Al(acind)3] complexes and spiro 2-CBP acted as acceptor and donor, respectively. These results suggest that [Al(acind)3] complexes have potential applications as molecular light converter materials for fabricating new electroluminescent devices.

In this work, synthesis, characterization and photophysical properties of trivalent rare earth complexes with a nonsteroidal anti-inflammatory drug [the indomethacinate (indo), presenting formulas RE(indo)3(H2O)x (x = 3, for Eu3+ and Gd+3, and x = 4 for Tb+3), RE(indo)3(bipy) and RE(indo)3(phen) (bipy: 2,2'-bipyridine, and phen: 1,10-phenanthroline)] were investigated. Based on photoluminescent results, the intramolecular energy transfer process from T1 triplet states of indo, phen and bipy ligands to the 5D0 emitting level of the Eu3+ ion in the coordination compounds is discussed. Accordingly, it is proposed two possible intramolecular energy transfer mechanisms between indomethacinate ligand and rare earth ions, which involve the participation of excited electronic states of the heterocyclic ligands as intermediate ones.

[RE(TLA)·(H2O)n:Eu3+] (RE3+: Y, Gd and Lu; TLA: trimellitic acid) precursor complexes were synthesized by an one step aqueous co-precipitation method. After annealing for 1 h, RE2O3:Eu3+ nanophosphors were formed through the benzenetricarboxylate low temperature thermolysis method (500-1000 ºC). The compounds were characterized by using different techniques [elemental analysis (CHN), Fourier transform infrared spectroscopy (FTIR), thermogravimetry (TG/DTG), X-ray powder diffraction (XPD) and scanning electron microscope (SEM)]. The XPD data indicated that the Y2O3:Eu3+ materials have crystallite size range from 11 to 62 nm. The SEM and transmission electron microscopy (TEM) images show that the annealed materials keep morphological similarities with the precursor complexes. The photoluminescence properties were studied based on the excitation and emission spectra, and luminescence decay lifetimes of the 5D0 emitting level of the Eu3+ ion. The experimental intensity parameters (Ωλ), lifetimes (τ), as well as radiative (Arad) and non-radiative (Anrad) decay rates were calculated and discussed. The RE2O3:Eu3+ phosphors (RE: Y3+ and Lu3+) annealed at 500 to 1000 ºC have emission quantum efficiency (intrinsic quantum yield) values from 60 to 82%, indicating that this material can be potentially used for optical markers applications.

Novos complexos indandionatos de fórmulas [Ln(aind)3L(H2O)] e [Ln(bind)3L]∙H2O, (L: 1,10-fenantrolina (phen) ou 4,7-dimetil-1,10-fenantrolina (dmphen), Ln3+: Eu3+ ou Gd3+, aind: 2-acetil-1,3-indandionato e bind: 2-benzoil-1,3-indandionato) foram sintetizados e caracterizados por análise elementar, espectroscopia de absorção na região do infravermelho e análise termogravimétrica. Os dados de caracterização são consistentes com a presença de uma molécula de água de cristalização nas estruturas dos compostos [Ln(bind)3L]∙H2O, enquanto que nos complexos [Ln(aind)3L(H2O)] a molécula de água atua como ligante. As geometrias dos complexos do íon Eu3+, otimizadas pelo modelo SPARKLE/AM1, foram consistentes com os resultados experimentais de luminescência. As propriedades luminescentes dos compostos de Eu3+ são discutidas em termos de parâmetros de intensidade experimentais (Ω2 e Ω4), taxas radiativas (Arad) e não-radiativas (Anrad) e eficiência quântica de emissão (η). Os maiores valores de η foram obtidos para os compostos [Eu(bind)3L]∙H2O, refletindo a ausência de moléculas de água na primeira esfera de coordenação do íon Eu3+.

Novel Ln3+-indandionate complexes of formulas [Ln(aind)3L(H2O)] and [Ln(bind)3L]∙H2O (L: 1,10-phenanthroline (phen) or 4,7-dimethyl-1,10-phenanthroline (dmphen), Ln3+: Eu3+ or Gd3+, aind: 2-acetyl-1,3-indandionate and bind: 2-benzoyl-1,3-indandionate) were synthesized and characterized by elemental analysis, infrared spectroscopy, and thermogravimetric analyses. The characterization data are consistent with the presence of a water lattice molecule in the [Ln(bind)3L]∙H2O compounds. However, the data also suggest that the water acts as a coordinated molecule in the [Ln(aind)3L(H2O)] ones. Theoretical geometries of the Eu3+-complexes have been optimized via the SPARKLE/AM1 Model for lanthanide complexes that are consistent with their luminescence experimental data. The photoluminescence properties of the Eu3+-compounds have been discussed in terms of experimental intensity parameters (Ω2 and Ω4), radiative (Arad), and non-radiative (Anrad) spontaneous emission coefficients. The higher values of emission quantum efficiency (η) of the [Eu(bind)3L]∙H2O compounds reflect the absence of luminescence-quenching water molecule in their first coordination spheres.

Este trabalho relata a síntese, a caracterização e as propriedades luminescentes dos complexos de fórmulas [Tb(DBM)3L], [Tb(DBM)2(NO3)L2)] e [Tb(DBM)(NO3)2(HMPA)2)] (DBM = dibenzoilmetanato; L: TPPO = óxido de trifenilfosfina ou HMPA = óxido de hexametilfosforamida). Os compostos foram caracterizados por análise elementar (CHN), titulação complexométrica com EDTA e espectroscopia no infravermelho com transformada de Fourier (FTIR), e as propriedades de fotoluminescência foram avaliadas. As energias dos estados tripletos do ligante DBM foram determinadas experimentalmente a partir dos espectros de fosforescência resolvidos no tempo dos compostos análogos do íon Gd3+. As energias aumentam em função do número de ânions nitratos que substituem o ligante DBM nos complexos. Ademais, os espectros de luminescência e os tempos de vida dos níveis emissores revelaram que a eficiência de transferência de energia ligante-metal segue a mesma tendência. Ao contrário dos complexos tris-DBM, o bis- e o mono-DBM apresentaram elevada intensidade de luminescência, sendo candidatos promissores para camadas emissoras de luz em dispositivos moleculares conversores de luz (LCMD).

The Tb3+-β-diketonate complexes [Tb(DBM)3L], [Tb(DBM)2(NO3)L2] and [Tb(DBM)(NO3)2(HMPA)2] (DBM = dibenzoylmethanate; L: TPPO = triphenylphosphine oxide or HMPA = hexamethylphosphine oxide) were prepared and characterized by elemental analysis (CHN), complexometric titration with EDTA and Fourier transform infrared (FTIR) spectroscopy, and the photoluminescence properties evaluated. The triplet state energies of the coordinated DBM ligands were determined using time-resolved phosphorescence spectra of analogous Gd3+ complexes. The results show that the energies increase along with the number of coordinated nitrate anions replacing the DBM ligand in the complexes. The luminescence spectra and emission lifetime measurements revealed that the ligand-to-metal energy transfer efficiency follows the same tendency. Unlike the tris-DBM complexes, bis- and mono-DBM presented high luminescence, and may act as promising candidates for preparation of the emitting layer of light converting molecular devices (LCMDs).

Os compostos Gd2(WO4)3:RE3+ (onde RE = Sm e Tb) preparados via métodos Pechini e cerâmico foram caracterizados por difratometria de raios-X e espectroscopia de absorção na região do infravermelho. Estes materiais de terras raras apresentam alta intensidade luminescente, laranja para os compostos de Sm3+ e verde para os de Tb3+, quando excitados com radiação UV. Os espectros de excitação dos compostos mostraram bandas largas oriundas da transferência de carga ligante-metal (O->W e O->RE3+) e bandas estreitas associadas às transições intraconfiguracionais (4f-4f). Os espectros de excitação do sistema com Tb3+ também exibiram bandas largas atribuídas à transição interconfiguracional (4f-5d). Quando os espectros de emissão dos compostos contendo Sm3+ e Tb3+ são obtidos com excitação no íon observa-se somente transições finas 4G5/2->6H J (J = 5/2, 7/2, 9/2 e 11/2) e 5D4-> 7F J (J = 0-6). Por outro lado, quando a excitação é monitorada na banda de transferência de carga (BTC, 270 nm) são também observadas bandas largas atribuídas a BTC (O->W). Os parâmetros de intensidade experimentais, etaSm e etaEu, apresentaram comportamentos similares, sugerindo que o íon Sm3+ encontra-se em um ambiente químico altamente polarizável e que o caráter covalente da interação metal-ligante é semelhante àquele do sistema tungstato de európio. O processo de relaxação cruzada baseado nos níveis 5D3 e 5D4 do sistema Gd2(WO4)3:Tb³ foi reportado.

The Gd2(WO4)3:RE3+ compounds (where RE3+ = Sm and Tb) were prepared by the Pechini and ceramic methods and characterized by X-ray diffraction and infrared spectroscopy. These rare earth materials present high orange (Sm3+-compound) and green (Tb3+-compound) luminescence intensity under UV radiation. The excitation spectra of these compounds presented broad bands arising from ligand-to-metal charge transfer (O->W and O->RE3+) and narrow bands from 4f-intraconfigurational transitions. The excitation spectra of Tb3+ system also exhibit broad bands attributed to the interconfigurational transition (4f-5d). The emission spectra exhibited the 4G5/2->6H J (J = 5/2, 7/2, 9/2 and 11/2) and 5D4-> 7F J (J = 0-6) transitions (direct excitation), for the systems doped with Sm3+ and Tb3+, respectively, while a broad band assigned to the LMCT (O->W) is observed when the excitation is monitored on the O->W LMCT state around 270 nm. The experimental intensity parameters etaSm and etaEu present similar behaviors, suggesting that the Sm3+ ion is in a highly polarizable chemical environment with similar covalent character of the metal-donor atom interaction to the tungstate doped europium system. The cross-relaxation process from the 5D3 to the 5D4 levels of the Gd2(WO4)3:Tb3+ system has been also reported.