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.

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.