Made available in DSpace on 2014-12-17T15:42:28Z (GMT). No. of bitstreams: 1 RoseaneSO_TESE.pdf: 2833413 bytes, checksum: cb4d0597d5a75ea4dc574237866165c1 (MD5) Previous issue date: 2013-07-30 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / This is a work involving fundamental studies of chemistry where the synthesis and structural characterization, as well as a possible future application of these new compounds as luminescent sensors or sunscreen agents, complexes with 4,4 diaminostilbene-2,2-disulfonic (DSD) and trivalent lanthanide ions La3+, Nd3+, Eu3+, Gd3+ and Yb3+, were synthesized in the ratio of 3 mmol: 1 mmol (DSD: lanthanides). The complexes obtained with these ions were present in powder form and were characterized by complexometric titration with EDTA CHN Elemental analysis, molecular absorption spectroscopy in the ultraviolet region, the absorption spectroscopy in the infrared, thermal analysis (TG / DTG), Nuclear Magnetic Resonance - NMR 1H and Luminescence Spectroscopy. The complexometric titration and CHN analysis, confirmed the TG / DTG which suggest that these complexes have the following general chemical formulas: [La2(C14H12S2O6N2)2(H2O)2Cl2].7H2O,[Nd2(C14H12S2O6N2)2(H2O)2Cl2].6H2O,[Eu2(C14 H12S2O6N2)2(H2O)2Cl2].7H2O,[Gd2(C14H12S2O6N2)2(H2O)2Cl2].4H2O e [Yb2(C14H12S2O6N2)2(H2O)2].6H2O. The disappearance of the bands in the infrared spectrum at 2921 cm-1 and 2623 cm-1 and the displacement of the bands in the spectra of the amine complex indicate that the lanthanide ion is coordinated to the oxygen atoms and the sulfonate groups of the nitrogens amines, suggesting the formation of the dimer. The disappearance of the signal and the displacement signal SO3H amines in the 1H NMR spectrum of this complex are also indicative coordination and dimer formation. The Thermogravimetry indicates that the DSD is thermally stable in the range of 40? to 385?C and their complexes with lanthanide ions exhibit weight loss between 4 and 5 stages. The Uv-visible spectra indicated that the DSD and complexes exhibit cis isomers. The analysis of luminescence indicates that the complexes do not exhibit emission in the region of the lanthanides but an intense emission part of the binder. This is related to the triplet states of the ligand, which are in the lowest energy state emitting lanthanide ions, and also the formation of the dimer that suppress the luminescence of ion Eu3+. The formation of dimer was also confirmed by calculating the europium complex structure using the model Hamiltonian PM6 and Sparkle / Visando um trabalho de estudos fundamentais da qu?mica, envolvendo a s?ntese e caracteriza??o estrutural, assim como uma poss?vel aplica??o futura desses novos compostos como sensores luminescentes ou agentes de prote??o solar, foram sintetizados os complexos com o ?cido 4,4-diaminoestilbeno-2,2-disulf?nico (DSD) e os ?ons lantan?deos trivalentes La3+, Nd3+, Eu3+, Gd3+ e Yb3+, preparados na propor??o de 3 mmol: 1mmol (DSD: Lantan?deos). Os complexos obtidos com esses ?ons apresentaram-se na forma de p? e foram caracterizados por: Titula??o Complexom?trica com EDTA, An?lise Elementar de CHN, Espectroscopia de Absor??o Molecular na Regi?o do Ultravioleta, Espectroscopia de Absor??o na Regi?o do Infravermelho, An?lise T?rmica (TG/DTG), Resson?ncia Magn?tica Nuclear RMN-1H e Espectroscopia de Luminesc?ncia. A titula??o complexom?trica e a an?lise de CHN, com confirma??o da TG/DTG, sugerem que esses complexos possuem as seguintes f?rmulas qu?micas gerais: [La2(C14H12S2O6N2)2(H2O)2Cl2].7H2O, [Nd2(C14H12S2O6N2)2(H2O)2Cl2].6H2O, [Eu2(C14H12S2O6N2)2(H2O)2Cl2].7H2O, [Gd2(C14H12S2O6N2)2(H2O)2Cl2].4H2O e [Yb2(C14H12S2O6N2)2(H2O)2].6H2O. O desaparecimento das bandas, no espectro de Infravermelho, em 2921 cm-1 e 2623 cm-1 e o deslocamento das bandas da amina nos espectros dos complexos indicam que a coordena??o ao ?on lantan?deo ocorre atrav?s dos oxig?nios dos grupos sulfonatos e pelos nitrog?nios das aminas, sugerindo a forma??o do d?mero. O desaparecimento do sinal SO2O-H e o deslocamento do sinal das aminas no espectro de RMN-1H dos complexos s?o tamb?m indicativos dessa coordena??o e da forma??o do d?mero. A an?lise t?rmica indica que o DSD ? termicamente est?vel no intervalo de 40?C at? 385?C e que os seus complexos com os ?ons lantan?deos apresentam perda de massa entre 4 e 5 etapas. Os espectros de Uv-Vis?vel indicam que DSD e os complexos apresentam isomeria cis. A an?lise de luminesc?ncia indica que os complexos n?o apresentam emiss?o na regi?o dos ?ons lantan?deos, mas sim uma emiss?o intensa da parte do ligante. Isso est? relacionado com os estados tripletos do ligante, que est?o em energia mais baixa que o estado emissor dos ?ons lantan?deos, e tamb?m com a forma??o do d?mero que suprime a luminesc?ncia do ?on Eu3+. A forma??o do d?mero tamb?m foi confirmada atrav?s do c?lculo da estrutura do complexo de eur?pio, utilizando o modelo Sparkle e hamiltoniano PM6, que mostrou um ponto de m?nimo na superf?cie de energia potencial desta esp?cie