Síntese e arranjos supramoleculares de complexos Bis(triazenido) macrocíclicos e triazenido 1-óxido com os cátions Cu2+, Ni2+, Cu+, K+
Autor(a) principal: | |
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Data de Publicação: | 2010 |
Tipo de documento: | Tese |
Idioma: | por |
Título da fonte: | Biblioteca Digital de Teses e Dissertações do UFSM |
Texto Completo: | http://repositorio.ufsm.br/handle/1/4189 |
Resumo: | This work elaborates on the determination of crystal and molecular structures of four pro-ligands, emphasizing bis(triazenes), triazene 1-oxide and a new class of bis(triazenes) macrocyclic, and eight complexes involving Cu+, Cu2 +, Ni2 + and K+. Pro-ligands triazenes 1-oxide are relatively small and simple molecules. When they are deprotonated they presen a high ability to form supramolecular assemblies, either because they are planar and facilitate the metal-metal approach and the formation of π···π interactions _ as in the case of complex (2) _, or because they have substituents with capacity of act as agent of secondary complexation forming polycationic structures _ as in the case of complex (3). Pro-ligand bis(triazenes) are double agents of complexation. The bis(triazene) (4) complexed Copper(I) forming a binuclear complex (5). The same ligand also led to binuclear complexes of Copper(II) through the chelate and macrocyclic effect, forming two types of crystal structures, one non-centrosymmetric (6), the other centrosymmetric (7). The pro-ligand bis(triazene) macrocyclic (8) has a cavity with ideal size for the complexation of transition metals, resulting, for example, in complex (9) with the cation Nickel(II). The ligand in this complex has substituents in para position. These substituents, two pyridine molecules (in the coordination sphere of the metal) and two pyridine molecules (as solvate of crystallization) form weak electrostatic interactions in the supramolecular arrangement. The bis(triazene) macrocyclic (10) has a central cavity larger than the bis(triazene) macrocyclic (8), allowing the complexation of larger molecules or ions. The analysis by X-ray diffraction on single crystal for the compound (10) revealed the presence of disordered water molecules inside the cavity, forming a chain of water molecules perpendicular to the stacked molecules of (10). When the compound (10) is deprotonated with a weak base such as pyridine, the deprotonation occurs partially, leading to a binuclear complex with Copper(II)-bridged μ2-OH (11). Two molecules of the ligand coordinate the two Copper(II) cations, and the coordination sphere is completed by two axial pyridine molecules. When the compound (10) is deprotonated with a strong base such as sodium or potassium ethanolate, the deprotonation occurs totally, leading to a binuclear conmplex with Copper(II)-bridged μ2-OCH2CH3 (12). One molecule ligand coordinates two Copper(II) cations and the coordination sphere is also supplemented by two axial pyridine molecules. The synthesis of a new class of macrocyclic triazenes has been successfully performed as well as the synthesis of their metallic complexes. The characterization of their structures and supramolecular assemblies was performed using the analysis by X-ray diffraction on single crystal and other secondary methods. |
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2017-05-102017-05-102010-06-09SANTOS, Aline Joana Rolina Wohlmuth Alves dos. Synthesis and supramolecular arrangements of bis(triazenide) macrocyclic and triazenide 1-oxide complexes with Cu2+, Ni2+, Cu+, K+ cations. 2010. 177 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2010.http://repositorio.ufsm.br/handle/1/4189This work elaborates on the determination of crystal and molecular structures of four pro-ligands, emphasizing bis(triazenes), triazene 1-oxide and a new class of bis(triazenes) macrocyclic, and eight complexes involving Cu+, Cu2 +, Ni2 + and K+. Pro-ligands triazenes 1-oxide are relatively small and simple molecules. When they are deprotonated they presen a high ability to form supramolecular assemblies, either because they are planar and facilitate the metal-metal approach and the formation of π···π interactions _ as in the case of complex (2) _, or because they have substituents with capacity of act as agent of secondary complexation forming polycationic structures _ as in the case of complex (3). Pro-ligand bis(triazenes) are double agents of complexation. The bis(triazene) (4) complexed Copper(I) forming a binuclear complex (5). The same ligand also led to binuclear complexes of Copper(II) through the chelate and macrocyclic effect, forming two types of crystal structures, one non-centrosymmetric (6), the other centrosymmetric (7). The pro-ligand bis(triazene) macrocyclic (8) has a cavity with ideal size for the complexation of transition metals, resulting, for example, in complex (9) with the cation Nickel(II). The ligand in this complex has substituents in para position. These substituents, two pyridine molecules (in the coordination sphere of the metal) and two pyridine molecules (as solvate of crystallization) form weak electrostatic interactions in the supramolecular arrangement. The bis(triazene) macrocyclic (10) has a central cavity larger than the bis(triazene) macrocyclic (8), allowing the complexation of larger molecules or ions. The analysis by X-ray diffraction on single crystal for the compound (10) revealed the presence of disordered water molecules inside the cavity, forming a chain of water molecules perpendicular to the stacked molecules of (10). When the compound (10) is deprotonated with a weak base such as pyridine, the deprotonation occurs partially, leading to a binuclear complex with Copper(II)-bridged μ2-OH (11). Two molecules of the ligand coordinate the two Copper(II) cations, and the coordination sphere is completed by two axial pyridine molecules. When the compound (10) is deprotonated with a strong base such as sodium or potassium ethanolate, the deprotonation occurs totally, leading to a binuclear conmplex with Copper(II)-bridged μ2-OCH2CH3 (12). One molecule ligand coordinates two Copper(II) cations and the coordination sphere is also supplemented by two axial pyridine molecules. The synthesis of a new class of macrocyclic triazenes has been successfully performed as well as the synthesis of their metallic complexes. The characterization of their structures and supramolecular assemblies was performed using the analysis by X-ray diffraction on single crystal and other secondary methods.Este trabalho apresenta as determinações das estruturas cristalinas/moleculares de quatro pró-ligantes, enfatizando bis(triazenos), triazeno 1-óxido e a nova classe de bis(triazenos) macrocíclicos, e oito complexos envolvendo os cátions Cu+, Cu2+, Ni2+ e K+. Pró-ligantes triazenos 1-óxido são moléculas relativamente pequenas e simples, que quando desprotonadas apresentam elevada capacidade de formação de arranjos supramoleculares, sejam pelo fato de serem planares e facilitarem a aproximação metal-metal e a formação de interações π···π, como no caso do complexo (2), ou pelo fato de apresentarem substituintes capazes de atuarem como complexantes secundários, formando estruturas policatiônicas complexas, como no caso do complexo (3). Pró-ligantes bis(triazenos) são agentes duplos de complexação. O bis(triazeno) (4) mostrou-se capaz de complexar o íon cobre(I) formando um complexo binuclear (5). O mesmo ligante, ainda, originou complexos binucleares de cobre(II), através do efeito quelato e macrocíclico, formando dois tipos de estruturas cristalinas, uma não-centrossimétrica (6) e outra centrossimétrica (7). O pró-ligante bis(triazeno) macrocíclico (8) apresenta uma cavidade com tamanho ideal para a complexação de metais de transição, originando, por exemplo, o complexo (9) com o cátion níquel(II). O ligante neste complexo apresenta substituintes em posição para e estes subtituintes, adicionados às moléculas de piridina que completam a esfera de coordenação do metal e às moléculas de piridina como solvato de cristalização, formam o arranjo supramolecular, através de interações eletrostáticas fracas. O pró-ligante bis(triazeno) macrocíclico (10) apresenta uma cavidade central maior que o pró-ligante bis(triazeno) macrocíclico (8), possibilitando a complexação de moléculas ou cátions maiores. A difração de raios-x em monocristal de (10) revelou a presença de moléculas de água desordenadas no interior da cavidade, formando uma cadeia perpendicular às moléculas empacotadas do pró-ligante macrocíclico. Quando o composto (10) é desprotonado com base fraca, como piridina, a desprotonação ocorre de maneira parcial, originando um complexo binuclear de cobre(II) unido por pontes μ2-OH (11), onde duas moléculas de ligante coordenam os dois íons cobre(II) e a esfera de coordenação quadrática é completada por duas moléculas de piridina axiais. Quando o composto (10) é desprotonado com base forte, como etóxido de sódio ou potássio, a desprotonação ocorre de maneira total, originando um complexo binuclear de cobre(II) unido por pontes μ2-OCH2CH3 (12), onde uma molécula de ligante coordena os dois íons cobre(II) e a esfera de coordenação quadrática também é completada por duas moléculas de piridina axiais. A síntese de mais representantes da nova classe de triazenos macrocíclicos foi realizada com sucesso neste trabalho, bem como a síntese de complexos, envolvendo triazenidos macrocíclicos. A caracterização de suas estruturas e arranjos supramoleculares foi realizada através de difração de raios-x em monocristal e outros métodos secundários.Coordenação de Aperfeiçoamento de Pessoal de Nível Superiorapplication/pdfporUniversidade Federal de Santa MariaPrograma de Pós-Graduação em QuímicaUFSMBRQuímicaTriazeno 1-óxidoBis(triazenos)Bis(triazenos) macrocíclicosArranjos supramolecularesComplexos de Cu+Cu2+Ni2+K+Triazene 1-oxideBis(triazenes)Bis(triazenes) macrocyclicSupramolecular assembliesComplexes of Cu+Cu2 +Ni2 +K+CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICASíntese e arranjos supramoleculares de complexos Bis(triazenido) macrocíclicos e triazenido 1-óxido com os cátions Cu2+, Ni2+, Cu+, K+Synthesis and supramolecular arrangements of bis(triazenide) macrocyclic and triazenide 1-oxide complexes with Cu2+, Ni2+, Cu+, K+ cationsinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisHörner, Manfredohttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4783542Z5Casagrande, Adriana Curi Aiubhttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4799650J2Back, Davi Fernandohttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4701590T6Burrow, Robert Alanhttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4761460Y1http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4718916U5Santos, Aline Joana Rolina Wohlmuth Alves dos1006000000004003003003003003007e7796b1-053d-4bbe-8e62-e769f0da5cea09991eee-a5b4-4498-ac52-7496827b0d154c611110-f33d-4144-9cd4-0154240b459cf33f5bf0-5193-4fac-992b-192381823da848da60b6-6eee-4326-918d-0e18011f227dinfo:eu-repo/semantics/openAccessreponame:Biblioteca Digital de Teses e Dissertações do UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSMORIGINALSANTOS, ALINE JOANA ROLINA WOHLMUTH ALVES DOS.pdfapplication/pdf18556303http://repositorio.ufsm.br/bitstream/1/4189/1/SANTOS%2c%20ALINE%20JOANA%20ROLINA%20WOHLMUTH%20ALVES%20DOS.pdf0147aaf2b7e26cb8686d38c139965368MD51TEXTSANTOS, ALINE JOANA ROLINA WOHLMUTH ALVES DOS.pdf.txtSANTOS, ALINE JOANA ROLINA WOHLMUTH ALVES DOS.pdf.txtExtracted texttext/plain296066http://repositorio.ufsm.br/bitstream/1/4189/2/SANTOS%2c%20ALINE%20JOANA%20ROLINA%20WOHLMUTH%20ALVES%20DOS.pdf.txt5f699c7ac44e792e3024b15cfb6607a4MD52THUMBNAILSANTOS, ALINE JOANA ROLINA WOHLMUTH ALVES DOS.pdf.jpgSANTOS, ALINE JOANA ROLINA WOHLMUTH ALVES DOS.pdf.jpgIM Thumbnailimage/jpeg5370http://repositorio.ufsm.br/bitstream/1/4189/3/SANTOS%2c%20ALINE%20JOANA%20ROLINA%20WOHLMUTH%20ALVES%20DOS.pdf.jpgdc6645704cd896111d19ac65b939bd6dMD531/41892017-07-25 11:05:12.153oai:repositorio.ufsm.br:1/4189Biblioteca Digital de Teses e Dissertaçõeshttps://repositorio.ufsm.br/ONGhttps://repositorio.ufsm.br/oai/requestatendimento.sib@ufsm.br||tedebc@gmail.comopendoar:2017-07-25T14:05:12Biblioteca Digital de Teses e Dissertações do UFSM - Universidade Federal de Santa Maria (UFSM)false |
dc.title.por.fl_str_mv |
Síntese e arranjos supramoleculares de complexos Bis(triazenido) macrocíclicos e triazenido 1-óxido com os cátions Cu2+, Ni2+, Cu+, K+ |
dc.title.alternative.eng.fl_str_mv |
Synthesis and supramolecular arrangements of bis(triazenide) macrocyclic and triazenide 1-oxide complexes with Cu2+, Ni2+, Cu+, K+ cations |
title |
Síntese e arranjos supramoleculares de complexos Bis(triazenido) macrocíclicos e triazenido 1-óxido com os cátions Cu2+, Ni2+, Cu+, K+ |
spellingShingle |
Síntese e arranjos supramoleculares de complexos Bis(triazenido) macrocíclicos e triazenido 1-óxido com os cátions Cu2+, Ni2+, Cu+, K+ Santos, Aline Joana Rolina Wohlmuth Alves dos Triazeno 1-óxido Bis(triazenos) Bis(triazenos) macrocíclicos Arranjos supramoleculares Complexos de Cu+ Cu2+ Ni2+ K+ Triazene 1-oxide Bis(triazenes) Bis(triazenes) macrocyclic Supramolecular assemblies Complexes of Cu+ Cu2 + Ni2 + K+ CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
Síntese e arranjos supramoleculares de complexos Bis(triazenido) macrocíclicos e triazenido 1-óxido com os cátions Cu2+, Ni2+, Cu+, K+ |
title_full |
Síntese e arranjos supramoleculares de complexos Bis(triazenido) macrocíclicos e triazenido 1-óxido com os cátions Cu2+, Ni2+, Cu+, K+ |
title_fullStr |
Síntese e arranjos supramoleculares de complexos Bis(triazenido) macrocíclicos e triazenido 1-óxido com os cátions Cu2+, Ni2+, Cu+, K+ |
title_full_unstemmed |
Síntese e arranjos supramoleculares de complexos Bis(triazenido) macrocíclicos e triazenido 1-óxido com os cátions Cu2+, Ni2+, Cu+, K+ |
title_sort |
Síntese e arranjos supramoleculares de complexos Bis(triazenido) macrocíclicos e triazenido 1-óxido com os cátions Cu2+, Ni2+, Cu+, K+ |
author |
Santos, Aline Joana Rolina Wohlmuth Alves dos |
author_facet |
Santos, Aline Joana Rolina Wohlmuth Alves dos |
author_role |
author |
dc.contributor.advisor1.fl_str_mv |
Hörner, Manfredo |
dc.contributor.advisor1Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4783542Z5 |
dc.contributor.referee1.fl_str_mv |
Casagrande, Adriana Curi Aiub |
dc.contributor.referee1Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4799650J2 |
dc.contributor.referee2.fl_str_mv |
Back, Davi Fernando |
dc.contributor.referee2Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4701590T6 |
dc.contributor.referee3.fl_str_mv |
Burrow, Robert Alan |
dc.contributor.referee3Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4761460Y1 |
dc.contributor.authorLattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4718916U5 |
dc.contributor.author.fl_str_mv |
Santos, Aline Joana Rolina Wohlmuth Alves dos |
contributor_str_mv |
Hörner, Manfredo Casagrande, Adriana Curi Aiub Back, Davi Fernando Burrow, Robert Alan |
dc.subject.por.fl_str_mv |
Triazeno 1-óxido Bis(triazenos) Bis(triazenos) macrocíclicos Arranjos supramoleculares Complexos de Cu+ Cu2+ Ni2+ K+ |
topic |
Triazeno 1-óxido Bis(triazenos) Bis(triazenos) macrocíclicos Arranjos supramoleculares Complexos de Cu+ Cu2+ Ni2+ K+ Triazene 1-oxide Bis(triazenes) Bis(triazenes) macrocyclic Supramolecular assemblies Complexes of Cu+ Cu2 + Ni2 + K+ CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
dc.subject.eng.fl_str_mv |
Triazene 1-oxide Bis(triazenes) Bis(triazenes) macrocyclic Supramolecular assemblies Complexes of Cu+ Cu2 + Ni2 + K+ |
dc.subject.cnpq.fl_str_mv |
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
This work elaborates on the determination of crystal and molecular structures of four pro-ligands, emphasizing bis(triazenes), triazene 1-oxide and a new class of bis(triazenes) macrocyclic, and eight complexes involving Cu+, Cu2 +, Ni2 + and K+. Pro-ligands triazenes 1-oxide are relatively small and simple molecules. When they are deprotonated they presen a high ability to form supramolecular assemblies, either because they are planar and facilitate the metal-metal approach and the formation of π···π interactions _ as in the case of complex (2) _, or because they have substituents with capacity of act as agent of secondary complexation forming polycationic structures _ as in the case of complex (3). Pro-ligand bis(triazenes) are double agents of complexation. The bis(triazene) (4) complexed Copper(I) forming a binuclear complex (5). The same ligand also led to binuclear complexes of Copper(II) through the chelate and macrocyclic effect, forming two types of crystal structures, one non-centrosymmetric (6), the other centrosymmetric (7). The pro-ligand bis(triazene) macrocyclic (8) has a cavity with ideal size for the complexation of transition metals, resulting, for example, in complex (9) with the cation Nickel(II). The ligand in this complex has substituents in para position. These substituents, two pyridine molecules (in the coordination sphere of the metal) and two pyridine molecules (as solvate of crystallization) form weak electrostatic interactions in the supramolecular arrangement. The bis(triazene) macrocyclic (10) has a central cavity larger than the bis(triazene) macrocyclic (8), allowing the complexation of larger molecules or ions. The analysis by X-ray diffraction on single crystal for the compound (10) revealed the presence of disordered water molecules inside the cavity, forming a chain of water molecules perpendicular to the stacked molecules of (10). When the compound (10) is deprotonated with a weak base such as pyridine, the deprotonation occurs partially, leading to a binuclear complex with Copper(II)-bridged μ2-OH (11). Two molecules of the ligand coordinate the two Copper(II) cations, and the coordination sphere is completed by two axial pyridine molecules. When the compound (10) is deprotonated with a strong base such as sodium or potassium ethanolate, the deprotonation occurs totally, leading to a binuclear conmplex with Copper(II)-bridged μ2-OCH2CH3 (12). One molecule ligand coordinates two Copper(II) cations and the coordination sphere is also supplemented by two axial pyridine molecules. The synthesis of a new class of macrocyclic triazenes has been successfully performed as well as the synthesis of their metallic complexes. The characterization of their structures and supramolecular assemblies was performed using the analysis by X-ray diffraction on single crystal and other secondary methods. |
publishDate |
2010 |
dc.date.issued.fl_str_mv |
2010-06-09 |
dc.date.accessioned.fl_str_mv |
2017-05-10 |
dc.date.available.fl_str_mv |
2017-05-10 |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/doctoralThesis |
format |
doctoralThesis |
status_str |
publishedVersion |
dc.identifier.citation.fl_str_mv |
SANTOS, Aline Joana Rolina Wohlmuth Alves dos. Synthesis and supramolecular arrangements of bis(triazenide) macrocyclic and triazenide 1-oxide complexes with Cu2+, Ni2+, Cu+, K+ cations. 2010. 177 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2010. |
dc.identifier.uri.fl_str_mv |
http://repositorio.ufsm.br/handle/1/4189 |
identifier_str_mv |
SANTOS, Aline Joana Rolina Wohlmuth Alves dos. Synthesis and supramolecular arrangements of bis(triazenide) macrocyclic and triazenide 1-oxide complexes with Cu2+, Ni2+, Cu+, K+ cations. 2010. 177 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2010. |
url |
http://repositorio.ufsm.br/handle/1/4189 |
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100600000000 |
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400 300 300 300 300 300 |
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Universidade Federal de Santa Maria |
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UFSM |
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Química |
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Universidade Federal de Santa Maria |
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