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Avaliação da auto-associação molecular de complexos metálicos com ligantes triazenidos derivados do 1,3-bis(fenil)triazeno / Evaluation of the molecular autoassociation of metallic complexes with triazenide derived from 1,3-bis (phenyl)triazene

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / This work presents the synthesis and the investigation of the crystalline and molecular structure of 1,3-bis(2-methoxy-4-nitrophenyl)triazene ethanol and seventeen new mononuclear or binuclear complexes of Cu(I), Cu(II), Tl(I), Hg(II), Ag(I), Ni(II), Zn (II) with monocatenated triazenide ligands derived from the 1,3-bis(phenyl)triazene. The coordination of metallic ions by triazenido compounds had been studied in the solid state. We studied the relations that make possible the formation of intramoleculares and intermoleculares interactions, that could show supramolecular arrangements unidimensionais, bidimensional and until three-dimensional. Other eight ligands had been synthesized and we investigated its physical and molecular properties: 1,3-bis (3-nitrophenyl)triazene, 1,3-bis(4-methoxycarbonylphenyl)triazene, 1,3-bis(4-ethoxycarbonylphenyl)triazene, 1,3-bis(4-chlorophenyl)-triazene, 1-(phenyl)-3-(4-nitrophenyl)triazene, 1-(4-chlorophenyl)-3-(4-nitrophenyl)triazene, 1-(2-methoxy-4-nitrophenyl)-3-(2,4-dibromophenyl)triazene and 1-(4-nitrophenyl)-3-(2-pyrimidinyl) triazene. We used techniques of Infrared Absorption Spectroscopy, Spectrometry of Nuclear Magnetic Resonance, Melting Point and Elementary Analysis CHN in this study. The variety in the geometry of coordination of the 1,3-bis(2-methoxy-4-nitrophenyl)triazene can be used to depicted its versatility to form complexes with many metallic ions, beyond presenting a variety of chemical and spectroscopic properties. The complexes {Cu[CH3O(NO2)C6H3NNNC6H3(NO2)OCH3]}4(CH3CN)4 (1), {Cu[CH3O(NO2)C6H3NNNC6H3(NO2)OCH3(C5H5N)2(N3)]}(3) and {Cu[CH3O(O2N)C6H3NNNC6H3(NO2)OCH3-(C5H5N)2(CH3COO)]} (4), using the copper ion (I and II) had been characterized by Spectroscopy of Electronic Paramagnetic Resonance, Electronic and Electrochemical Spectroscopy. All these complexes of Cu (II) had presented interesting magnetic and electrochemical properties. / Este trabalho apresenta a síntese e a investigação da estrutura cristalina e molecular do préligante 1,3-bis(2-metoxi-4-nitrofenil)triazeno etanol e de dezessete novos complexos mononucleares e binucleares de Cu(I), Cu(II), Tl(I), Hg(II), Ag(I), Ni(II), Zn(II) com ligantes triazenídicos monocatenados derivados do 1,3-bis(fenil)triazeno. Estudou-se compostos triazenídicos coordenados a íons metálicos em estado sólido, avaliando-se as interações que possibilitam a formação de ligações não-clássicas intra e intermoleculares, resultando os arranjos supramoleculares unidimensionais, bidimensionais e até tridimensionais. Outros oito pré-ligantes foram sintetizados e investigados as suas propriedades físicas e moleculares: 1,3-bis(3-nitrofenil)triazeno, 1,3-bis(4-metoxicarbonilfenil)triazeno, 1,3-bis(4-etoxicarbonilfenil)-triazeno, 1,3-bis(4-clorofenil)triazeno, 1-(fenil)-3-(4-nitrofenil)triazeno, 1-(4-clorofenil)-3-(4-nitrofenil)triazeno, 1-(2-metoxi-4-nitrofenil)-3-(2,4-dibromofenil)triazeno e 1-(4-nitrofenil)-3-(2-pirimidinil)triazeno; utilizando técnicas de Espectroscopia de Infravermelho, Espectrometria de Ressonância Magnética Nuclear de Prótons, Ponto de Fusão e Análise Elementar CHN. A variedade de modo de coordenação que o pré-ligante 1,3-bis(2-metoxi-4-nitrofenil)triazeno pode exemplificar, destaca-se pela sua versatilidade de formar complexos com diversos íons metálicos, além de apresentar uma gama de propriedades químicas e espectroscópicas. Os complexos {Cu[CH3O(NO2)C6H3NNNC6H3(NO2)OCH3]}4(CH3CN)4 (1), {Cu[CH3O(NO2)C6H3N-NNC6H3(NO2)OCH3(C5H5N)2(N3)]} (3) e {Cu[CH3O(O2N)C6H3NNNC6H3(NO2)OCH3(C5H5N)2(CH3COO)]} (4) envolvendo o íon de cobre (I e II) foram caracterizados por Espectroscopia de Ressonância Paramagnética Eletrônica, Espectroscopia Eletrônica e Eletroquímica. Todos estes complexos de Cu(II) apresentaram interessantes propriedades magnéticas e eletroquímicas.

Identiferoai:union.ndltd.org:IBICT/oai:repositorio.ufsm.br:1/4141
Date13 September 2007
CreatorsVillis, Paulo Cesar Mendes
ContributorsHörner, Manfredo, Gushikem, Yoshitaka, Casagrande Junior, Osvaldo de Lazaro, Nakagaki, Shirley, Fenner, Herton
PublisherUniversidade Federal de Santa Maria, Programa de Pós-Graduação em Química, UFSM, BR, Química
Source SetsIBICT Brazilian ETDs
LanguagePortuguese
Detected LanguageEnglish
Typeinfo:eu-repo/semantics/publishedVersion, info:eu-repo/semantics/doctoralThesis
Formatapplication/pdf
Sourcereponame:Repositório Institucional da UFSM, instname:Universidade Federal de Santa Maria, instacron:UFSM
Rightsinfo:eu-repo/semantics/openAccess
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