Foto e eletroluminescência de complexos de samário, európio e gadolínio trivalentes com a beta-dicetona tta e o fosfinóxido quelante dppmo
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Data
2010-06-01
Autores
Monteiro, Jorge Henrique Santos Klier [UNESP]
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Universidade Estadual Paulista (Unesp)
Resumo
A síntese e o estudo da luminescência dos complexos [Ln(tta)3(dppmo)], sendo Ln = Sm3+, Eu3+ e Gd3+, tta = tenoiltrifluoroacetonato e dppmo = bis(difenilfosfino)metano dióxido são descritos neste trabalho. O ligante (dppmo) foi obtido através da oxidação do bis(difenilfosfino)metano (dppm) e utilizado como reagente para substituição das moléculas de água do aquo complexo [Ln(tta)3(H2O)2] precursor. A coordenação dos ligantes foi indicada pelo deslocamento para menores energias dos estiramentos dos grupos C=O e P=O. A estequiometria foi confirmada por titulação complexométrica da Ln3+ e análise elementar de carbono e de hidrogênio. A análise termogravimétrica indicou que não há perda de massa relativa a água e que o composto sintetizado possui uma boa estabilidade térmica. Através do espectro de emissão do complexo de gadolínio foi determinado o tripleto mais intenso do sistema em 1,840.104 cm-1. O espectro de emissão do complexo de európio apresenta transições 5D0 _ 7FJ (J = 0; 1; 2; 3 e 4) sendo a transição 5D0 _ 7F0 uma única linha indicando somente um sítio emissor sem centro de inversão. Do espectro de emissão foram determinados os parâmetros de intensidade _2, _4, R02 e Arad e a partir da curva de decaimento do estado emissor o tempo de vida (_) de 0,52 ms. A taxa de emissão total foi calculada a partir do inverso do tempo de vida e a eficiência quântica pela relação entre a taxa de emissão radiativa e não radiativa obtendo-se _ = 47%. O espectro de emissão do complexo de samário apresentou as linhas características 4G5/2 _ 6HJ (J = 5/2; 7/2; 9/2 e 11/2) sendo a transição 4G5/2 _ 6H9/2 de maior intensidade no espectro. O aumento do tempo de vida do estado emissor indica que as perdas por processos não-radiativos são minimizadas em relação ao aquo complexo precursor. Foram determinadas: geometria teórica utilizando o modelo Sparkle / AM1...
The synthesis and the luminescence study of complexes [Ln(tta)3(dppmo)], with Ln = Sm3+, Eu3+ and Gd3+, tta = thenoyltrifluoroacetonate and dppmo = bis(diphenylphosphine)methane dioxide are reported. The ligand (dppmo) was obtained by oxidation of bis(diphenylphosphine)methane and used as reagent to substitute the water molecules of aquo complex precursor [Ln(tta)3(H2O)2]. The ligand coordination was showed by the shift to low wavenumbers of C=O and P=O stretchings. The stoichiometry was confirmed by complexometric titration of Ln3+ and elemental analysis of carbon and hydrogen. The thermogravimetric analysis showed that there is no water molecules weight loss and that the complex has a good thermal stability. The most intense triplet of the system was determined in 1.804x104 cm-1 through the gadolinium emission spectrum. The europium complex emission spectrum presented the transitions 5D0 _ 7FJ (J = 0; 1; 2; 3 and 4) with only one line for transition 5D0 _ 7F0 showing that there is only one noncentrossymetric site. The intensity parameters _2, _4, R02 and Arad were determined from emission spectrum while the lifetime (_) was determined from decay curve and its value is 0.53 ms. The total emission rate was calculated from the inverse of lifetime and the quantum efficiency by relation between radiative emission rate and total emission rate obtaining _ = 47%. The emission spectrum of samarium complex presented the transitions 4G5/2 _ 6HJ (J = 5/2; 7/2; 9/2 and 11/2) with the most intense transition 4G5/2 _ 6H9/2 one. The lifetime increasing compared with that of aquo complex precursor shows that the non-radiative quenching is minimized. The ground state geometry and theoretical UV-vis absorption spectrum were determined using the Sparkle / AM1 implemented in Mopac2009 package. Transfer and back transfer energy rates from ligand to rare earth, the population of fundamental singlet, excited... (Complete abstract click electronic access below)
The synthesis and the luminescence study of complexes [Ln(tta)3(dppmo)], with Ln = Sm3+, Eu3+ and Gd3+, tta = thenoyltrifluoroacetonate and dppmo = bis(diphenylphosphine)methane dioxide are reported. The ligand (dppmo) was obtained by oxidation of bis(diphenylphosphine)methane and used as reagent to substitute the water molecules of aquo complex precursor [Ln(tta)3(H2O)2]. The ligand coordination was showed by the shift to low wavenumbers of C=O and P=O stretchings. The stoichiometry was confirmed by complexometric titration of Ln3+ and elemental analysis of carbon and hydrogen. The thermogravimetric analysis showed that there is no water molecules weight loss and that the complex has a good thermal stability. The most intense triplet of the system was determined in 1.804x104 cm-1 through the gadolinium emission spectrum. The europium complex emission spectrum presented the transitions 5D0 _ 7FJ (J = 0; 1; 2; 3 and 4) with only one line for transition 5D0 _ 7F0 showing that there is only one noncentrossymetric site. The intensity parameters _2, _4, R02 and Arad were determined from emission spectrum while the lifetime (_) was determined from decay curve and its value is 0.53 ms. The total emission rate was calculated from the inverse of lifetime and the quantum efficiency by relation between radiative emission rate and total emission rate obtaining _ = 47%. The emission spectrum of samarium complex presented the transitions 4G5/2 _ 6HJ (J = 5/2; 7/2; 9/2 and 11/2) with the most intense transition 4G5/2 _ 6H9/2 one. The lifetime increasing compared with that of aquo complex precursor shows that the non-radiative quenching is minimized. The ground state geometry and theoretical UV-vis absorption spectrum were determined using the Sparkle / AM1 implemented in Mopac2009 package. Transfer and back transfer energy rates from ligand to rare earth, the population of fundamental singlet, excited... (Complete abstract click electronic access below)
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Palavras-chave
Química inorgânica, Metais de terras raras, Luminescencia, Luminescence
Como citar
MONTEIRO, Jorge Henrique Santos Klier. Foto e eletroluminescência de complexos de samário, európio e gadolínio trivalentes com a beta-dicetona tta e o fosfinóxido quelante dppmo. 2010. 105 f. Dissertação (mestrado) - Universidade Estadual Paulista, Instituto de Química, 2010.