Propriedades estruturais e espectroscópicas de complexos de difenilfosfinatos dos sistemas ternários 'LA'-'CE'-'EU'/'LA'-CE'-'TB'
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2014-09-26
Autores
Rosa, Luis Henrique Zacari Rodrigues [UNESP]
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Universidade Estadual Paulista (Unesp)
Resumo
Complexos de lantanídeos trivalentes com ligantes difenilfosfinatos apresentam elevada estabilidade química e térmica. Esses tipos de complexos podem ser aplicados em dispositivos luminescentes, já que podem apresentar elevado rendimento quântico para a conversão de radiação ultravioleta em luz visível. Além disso, estes sistemas apresentam características de estrutura polimérica, na qual supõe-se a ocorrência de dois sítios cristalográficos de lantanídeos: (i) um centro simétrico e (ii) outro não centro simétrico. Esse trabalho tem por objetivo analisar as propriedades estruturais e espectroscópicas de sistemas ternários de difenilfosfinatos de lantânio (La3+), cério (Ce3+) e európio (Eu3+) ou térbio (Tb3+), principalmente no que se refere ao comportamento de emissão de luz pela excitação dos materiais com raios X (XEOL). Os compostos foram obtidos por precipitação em meio etanólico a partir do ácido difenilfosfínico e dos respectivos cloretos de lantanídeos. Por meio das espectroscopias vibracionais, tanto na região do infravermelho, como de espalhamento Raman, observou-se que a complexação ocorre preferencialmente através dos oxigênios do grupo fosforila, e que possivelmente as bandas de estiramento simétrico e assimétrico da ligação Ln-O encontram-se em 159 e 192 cm-1, respectivamente. A difração de raios X indicou que os complexos são isoestruturais, com o pico de maior intensidade em torno de 7º. Além disso, observou-se uma diminuição da cristalinidade conforme incrementa-se Ce3+ à matriz de lantânio. A morfologia dos compostos apresentou aglomerados sem uma forma definida, conforme estudos por microscopia eletrônica de varredura. Das análises por espectroscopia de reflectância difusa, observaram-se absorções em 220-270 nm, referentes a transição ? ? ?*, na região de 350-380 nm, a transição n ? ?* do ligante, e em 307 nm a...
Trivalent lanthanide complexes with diphenylphosphinate ligands present high chemical and thermal stability. Such complexes can be applied to luminescent devices, as they can present a high quantum yield for converting ultraviolet radiation into visible light. Moreover, these systems submit polymeric structure characterisics, in which it is assumed two crystallographic lanthanides sites: (i) a symmetrical center and (ii) other non-symmetrical center. This work aims to analyze the structural and spectroscopic properties of ternary systems diphenylphosphinates lanthanum (La3+), cerium (Ce3+) and europium (Eu3+) or terbium (Tb3+), especially with regard to the behavior of light emission by materials excitation by X rays (XEOL). The compounds were obtained by precipitation in ethanolic medium from diphenylphosphinic acid and its lanthanide chlorides. Via vibrational spectroscopy, both in IR region, as Raman scattering, was observed that complexation preferably occurs through the oxygens of phosphorylates group, and possibly symmetric and asymmetric stretch bands of Ln-O bond are at 159 and 192 cm-1. The X ray diffraction indicated that the complexes are isostructural, with the greatest intensity peak of around 7º. Furthermore, there was a decrease in the crystallinity when Ce3+ is incremented in the lanthanum matrix. The compounds morphology showed clusters without a definite form, according to studies by scanning electron microscopy. By diffuse reflectance spectroscopy, absorptions were noted at 220-270 nm, related to ???* transition, the n??* transition of the binder in 350-380 nm region, and the 4f?5d transition of the Ce3+ ion in 307 nm. From thermal analysis, data with analogous compounds stoichiometry metal:binder 1:3, infers a possible formation of chains containing two different lanthanides sites in the repeating unit polymer of formula [Ln2(dpp)6]n. Finally, had an optical study of...
Trivalent lanthanide complexes with diphenylphosphinate ligands present high chemical and thermal stability. Such complexes can be applied to luminescent devices, as they can present a high quantum yield for converting ultraviolet radiation into visible light. Moreover, these systems submit polymeric structure characterisics, in which it is assumed two crystallographic lanthanides sites: (i) a symmetrical center and (ii) other non-symmetrical center. This work aims to analyze the structural and spectroscopic properties of ternary systems diphenylphosphinates lanthanum (La3+), cerium (Ce3+) and europium (Eu3+) or terbium (Tb3+), especially with regard to the behavior of light emission by materials excitation by X rays (XEOL). The compounds were obtained by precipitation in ethanolic medium from diphenylphosphinic acid and its lanthanide chlorides. Via vibrational spectroscopy, both in IR region, as Raman scattering, was observed that complexation preferably occurs through the oxygens of phosphorylates group, and possibly symmetric and asymmetric stretch bands of Ln-O bond are at 159 and 192 cm-1. The X ray diffraction indicated that the complexes are isostructural, with the greatest intensity peak of around 7º. Furthermore, there was a decrease in the crystallinity when Ce3+ is incremented in the lanthanum matrix. The compounds morphology showed clusters without a definite form, according to studies by scanning electron microscopy. By diffuse reflectance spectroscopy, absorptions were noted at 220-270 nm, related to ???* transition, the n??* transition of the binder in 350-380 nm region, and the 4f?5d transition of the Ce3+ ion in 307 nm. From thermal analysis, data with analogous compounds stoichiometry metal:binder 1:3, infers a possible formation of chains containing two different lanthanides sites in the repeating unit polymer of formula [Ln2(dpp)6]n. Finally, had an optical study of...
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Palavras-chave
Fotoluminescencia, Cintiladores, Metais de terras raras, Compostos de coordenação, Photoluminescence
Como citar
ROSA, Luis Henrique Zacari Rodrigues. Propriedades estruturais e espectroscópicas de complexos de difenilfosfinatos dos sistemas ternários 'LA'-'CE'-'EU'/'LA'-CE'-'TB'. 2014. 105 f. Dissertação (mestrado) - Universidade Estadual Paulista, Instituto de Química, 2014.