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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
1

Síntese, caracterização e estrutura cristalina de redes metalorgânicas com ligantes mistos N- e O- doadores

Flores, Leonã da Silva 21 August 2015 (has links)
Submitted by Renata Lopes (renatasil82@gmail.com) on 2016-01-05T09:56:54Z No. of bitstreams: 1 leonadasilvaflores.pdf: 7703560 bytes, checksum: 6e5f7330b9f5bb6e7d5e649e91d606e6 (MD5) / Approved for entry into archive by Adriana Oliveira (adriana.oliveira@ufjf.edu.br) on 2016-01-25T16:05:33Z (GMT) No. of bitstreams: 1 leonadasilvaflores.pdf: 7703560 bytes, checksum: 6e5f7330b9f5bb6e7d5e649e91d606e6 (MD5) / Made available in DSpace on 2016-01-25T16:05:33Z (GMT). No. of bitstreams: 1 leonadasilvaflores.pdf: 7703560 bytes, checksum: 6e5f7330b9f5bb6e7d5e649e91d606e6 (MD5) Previous issue date: 2015-08-21 / CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / O objetivo deste trabalho foi o de sintetizar MOFs com ligantes mistos, N- e O- doadores, utilizando alguns cátions metálicos da primeira série de transição como conectores de rede. Foram obtidas as redes de coordenação CoPDC2D e ZnPDC2D, que são isoestruturas as quais se estendem bi-dimensionalmente. Essas formam laços com 16-circuitos (circuitos mais curtos que contemplam 16 átomos), e incluem apenas o ligante 2,5-piridinodicarboxilato 2,5-pdc e os cátions (Co2+ e Zn2+) na coordenação. Algumas diferenças entre as sínteses aqui reportadas e aquelas publicadas são mostradas. Este trabalho também reporta brevemente o estudo topológico dessas redes bidimensionais. Todavia, foi obtida uma nova rede de coordenação ZnPDC1D, envolvendo a formação de laço (circuitos mais curtos de átomos), os quais se estendem unidimensionalmente, e envolvem os cátions Zn2+ e o ligante 2,5-pdc. Além disso, foi reportada uma série de novos complexos CuPDC0D, MnPDC0D, CuPDC0Dq e CuPDC0Dr, aniônicos, envolvendo apenas o ligante 2,5-pdc e os íons Cu2+ e Mn2+. Estes sistemas formam monômeros, MnPDC0D e CuPDC0Dr, ou dímeros oxo-metalatos, CuPDC0D e CuPDC0Dq, e contemplam cátions etilenodimina na rede cristalina, formando complexos metálicos (no caso do CuPDC0Dq. Finalmente, faz-se uma discussão sobre os ligantes nitrogenados 1,2-bis(2-piridil)etilenediamina 2-bpen e 1,2-bis(4-piridil)etilenediamina 4-bpen, que foram sintetizados, porém não foi observada a coordenação destes em nenhum dos sistemas aqui reportados. Tal fato foi atribuído à hidrólise dos ligantes nitrogenados (Bases de Schiff) e, portanto, foi proposto um mecanismo para essa hidrólise nos sistemas obtidos. A estrutura cristalina do ligante 2-bpen, ainda não reportada na literatura, foi discutida. / The aim of this work was the synthesis of MOFs with mixed ligands N- and O- donors from some metal cations of first series transition, as connectors of the net. In this work has been obtained coordination networks CoPDC2D and ZnPDC2D, that are iso-structures, which extend two-dimensionally forming loops with 16-shortest circuits, including the ligand 2,5-pyridinedicarboxylate 2,5-pdc and the Co2+ and Zn2+ cations, respectively. Both structures were recently published, however there some differences between the syntheses and the yield. Moreover, this work reports briefly the topological study of these two-dimensional networks. Additionally, were obtained a new coordination network ZnPDC1D, including loops formation, which extend one-dimensionally containing the cation Zn2+ and 2,5-pdc ligand. Here, were reported a series of new complexes CuPDC0D, MnPDC0D, CuPDC0Dq and CuPDC0Dr, anionic, including just the 2-5-pdc ligand and some this having Cu2+ e Mn2+ ions. This systems are monomers MnPDC0D and CuPDC0Dr or oxometalates dimmers CuPDC0D and CuPDC0Dq, including etilenodiamine on the crystalline network and, in some cases, participating on coordination CoPDC0Dq. Finally, are discussed about the nitrogenous ligands 1,2-bis(2-pyridil)etilenediamine 2-bpen and 1,2-bis(4-pyridil)etilenediamine 4-bpen, that were synthesized and characterized but not was observed the coordination in any system here reported. This has been attributed to the hydrolysis of nitrogenous ligands and, therefore, was proposed a mechanism for hydrolysis of these systems. The crystal structure of ligand 2-bpen, not yet reported in literature, was discussed.

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