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).

Neste trabalho relatamos o uso de nitratos de lantanídeos [Ln(NO3)3] atuando como catalisador na síntese de uma única etapa de derivados de 3-benzoíla- e 3-acetila-1,2,4-oxadiazóis a partir de cetonas, nitrilas e ácido nítrico. Este é o primeiro exemplo da síntese em única etapa de preparação de derivados benzoíla e acetila-1,2,4-oxadiazóis, usando acetofenonas com grupos doadores de elétrons.

In this work we report the use of lanthanide nitrates [Ln(NO3)3] acting as catalyst in direct one-pot synthesis of 3-benzoyl- and 3-acetyl-1,2,4-oxadiazoles derivatives from ketones, nitriles and nitric acid. This is the first example of one-pot synthesis of benzoyl- and acetyl 1,2,4-oxadiazoles derivatives preparation using acetophenones derivates with electron-donator groups.

Uma nova classe de complexos ditiocarbamato de lantanídeo foi usada para promover a cianosililação de aldeídos com elevados rendimentos à temperatura ambiente. Esta é a primeira aplicação de ditiocarbamato de lantanídeo atuando como ácido de Lewis.

A new class of lanthanide dithiocarbamate complexes was used to promote the cyanosilylation of aldehydes at high yields at room temperature. This represents the first application of lanthanide dithiocarbamate acting as Lewis acid.