Die Immobilisierung homogener Katalysatoren ist eine wichtige Methode zur Realisierung der Abtrennbarkeit und Wiederverwendbarkeit aktiver Spezies. Im Rahmen dieser Arbeit wurde durch die Komplexierung von Palladium mit 1,4-Bis-(4′-pyrazolyl)benzen ein neues mikroporöses Koordinationspolymer generiert und dieses als heterogener Katalysator in der Suzuki-Miyaura-Kreuzkupplungsreaktion erfolgreich eingesetzt. Dabei konnten vollständige Umsätze und hohe Selektivitäten erzielt werden, die vergleichbar zu bereits kommerziell erhältlichen homogenen Katalysatoren sind. Die Besonderheit des Katalysators ist, neben dessen außergewöhnlich hohen chemischen Stabilität, die Variation seiner Struktureigenschaften durch die Wahl der Synthesebedingungen und die damit verbundene Steuerung seiner katalytischen Aktivität.

Le premier volet de ce travail portera sur l’expérience acquise lors d’un stage d’étude à Tokyo, au Japon, dans le groupe de recherche du Pr. Makoto Fujita, une sommité d’envergure internationale dans le domaine de l’auto-assemblage. En continuité avec les plus récents travaux du Pr. Fujita, des systèmes poreux auto-assemblés présentant des cavités fonctionnalisées ont été développés dans le but d’encapsuler des acides gras afin d’en déterminer la structure cristalline. Ces éponges ont été caractérisées par des techniques courantes telles que la spectroscopie à résonance magnétique nucléaire 1H, 13C{1H} et Cosy, la spectrométrie de masse, l’analyse élémentaire, la microscopie optique infrarouge ainsi que la diffraction des rayons X. Une autre approche employée pour obtenir de meilleures propriétés spectroscopiques fut la synthèse de dendrimères métalliques de génération 0. Un nouveau ligand de type 1,3,5-triazine a été synthétisé par une réaction typique de cyclisation de nitrile en présence catalytique d’hydrure de sodium. Des espèces mono-, bis- et trinucléaire de Ru(II) furent synthétisés ainsi que deux espèces hétérométalliques de Ru(II)/Pt(II) et de Ru(II)/Os(II). Tous les complexes obtenus furent caractérisés par spectroscopie à résonance magnétique nucléaire (1H, 13C{1H} et Cosy) à l’état liquide, par spectroscopie de masse à haute résolution et par analyse élémentaire. La génération de dihydrogène à partir de l’espèce hétérométallique a été étudiée. Les propriétés optiques et électroniques ont été analysées par spectroscopie UV-Vis, par analyse de la luminescence, du temps de vie de luminescence, par des analyses de rendement quantique ainsi que par des analyses de voltampérométrie cyclique à balayage. Finalement, dans le but d’améliorer les propriétés spectroscopiques d’absorption de complexes métalliques, nous avons synthétisé une série de polymères homo- et hétérométalliques, intégrant des ligands de type bis(2,2’:6,2’’-terpyridine). Les complexes générés furent caractérisés par diverses techniques tel que la spectroscopie à résonance magnétique nucléaire (1H, 13C{1H} et Cosy) à l’état liquide, par spectroscopie de masse à haute résolution ainsi que par analyse élémentaire. Les propriétés optiques et électroniques ont été analysées par spectroscopie UV-Vis, par analyse de la luminescence, du temps de vie de luminescence, par des analyses de rendement quantique ainsi que par des analyses de voltampérométrie cyclique à balayage. / It is well known that the self-assembly of small molecules into macromolecular species gives rise to an amplification and amelioration of their general properties. A first section on self-assembly will emphasize the acquired experience during an internship in Tokyo, Japan, in Pr. Makoto Fujita’s research group, a worldwide Figure in the area of self-assembly. Concomitant with the latest results obtained in Pr. Fujita research group on the self-assembly of molecular sponges, studies on molecular sponges with functionalized cavities will be presented. Such sponges were used to encapsulate fatty acids in order to determine their crystal structure. The sponges were characterized in different ways, such as 1H and 13C NMR, mass spectrometry, elemental analysis, optical microscopy coupled with infrared detection as well as X-ray diffraction. Another path of investigation to gain good spectroscopic properties is to synthesize metallodendrimers. A new 1,3,5-triazine ligand was synthesized by a typical nitrile cyclization in the presence of sodium hydride. Mono-, bis- and trimetallic Ru(II) species as well as heterometallic Ru(II)/Pt(II) and Ru(II)/Os(II) complexes were synthesized. All the complexes were characterized by nuclear magnetic resonance spectroscopy (1H, 13C{1H} and Cosy NMR) in the liquid state, high-resolution mass spectrometry, elemental analysis as well as X-ray diffraction in some cases. Attempts to generate H2 with the heterometallic species as catalysts have been investigated. The optical and electronic properties were also investigated by UV-Vis spectroscopy, luminescence analysis, excited state lifetimes, quantum yield efficiency and cyclic voltammetry.Finally, with the goal of having enhance light absorption, we synthesized a series of homo- and heterometallic coordination polymers with a ligand of the “back-to-back” terpyridine type. The complexes obtained were characterized by various techniques, such as nuclear magnetic resonance spectroscopy, high-resolution mass spectrometry as well as elementary analysis. The optical as well as the electronic properties were also investigated, using luminescence spectroscopy, excited state lifetime analysis, quantum yield determination and by cyclic voltammetry.

No description available.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The Hyptis pectinata (L.) Poit is a medicinal plant widely used in the Sergipe state for the treatment of skin illnesses, gastric clutter, nasal congestion and inflammation caused for bacteria and fungi. Hyptis pectinata, as well as other medicinal plants, can be contaminated with pesticides that are used in the agriculture, and residues cause damages to the man and the environment, due the toxicity of these products. In Brazil values of maximum residue limits (LMR) have not yet been established for pesticides in medicinal plants. In a similar way, it has little information about to the degree of contamination of these phytotherapic resources. Therefore, analytical methods have been developed for determination of residues in medicinal plants, with intention to assure the health of the population. In this context, this work considered the development of an analytical method for the extraction of pyrimethanil, ametryn, dichlofluanid, tetraconazole, flumetralin, kresoxim-methyl and tebuconazole from the medicinal plant Hyptis pectinata using the matrix solid-phase dispersion (MSPD) and gas chromatography-mass spectrometry (GC/MS). Therefore, in the present study, the aim was evaluating the combinations adsorvent/solvent (silica gel, Florisil®, neutral alumina and coordination polymers [Zn(BDC)(H2O)2]n, CuBTC and MIL-53/dichloromethane, dichloromethane:ethyl acetate (1:1, v/v) and ethyl acetate), for the simultaneous extraction of these pesticides. Amongst the evaluated combinations, the on consisting of 0.5 g of C18 and 20 mL of dichloromethane was most efficient, getting recoveries between 85 and 127%, with relative standard between 4 and 15%, in the levels of concentration 0.05; 0.1; 0.5 and 1.0 μg g-1. The linearity was above 0.9987 and the limits of detection between 0.02 and 0.07 μg g-1 and of quantification, 0.05 and 0.1 μg g-1. Among the polymeric phases (CuBTC, MIL-53 and [Zn(BDC)(H2O)2]n), [Zn(BDC) (H2O)2]n was most efficient in the extraction of pyrimethanil (83%), ametrin (95%), dichlofluanid (90%), tetraconazole (81%), flumetralin (74%) and kresoximmethyl (94%), being therefore a viable alternative to the adsorvent commercial conventional C18. / Hyptis pectinata (L.) Poit (Sambacaitá) é uma planta medicinal muito utilizada no estado de Sergipe para o tratamento de doenças de pele, desordem gástrica, rinofaringite, congestão nasal, febre e várias infecções causadas por bactérias e fungos. A Hyptis pectinata, assim como outras plantas medicinais, estão sujeitas a contaminação por pesticidas que são utilizados na agricultura, cujos resíduos podem causar danos ao homem e ao meio ambiente, devido à elevada toxicidade desses produtos. No Brasil não há valores de limites máximos de resíduos (LMR) estabelecidos para pesticidas em plantas medicinais. Do mesmo modo, há pouca informação quanto ao grau de contaminação destes recursos fitoterápicos. Portanto, métodos analíticos têm de ser desenvolvidos para determinação de resíduos em plantas medicinais, com intuito de assegurar a saúde da população. Neste contexto, este trabalho propôs o desenvolvimento de um método analítico para a determinação de pirimetanil, ametrina, diclofluanida, tetraconazol, flumetralina, cresoxim-metílico e tebuconazol em Hyptis pectinata, empregando a dispersão da matriz em fase sólida (DMFS) e cromatografia gasosa acoplada a espectrometria de massas (CG/EM). Para tanto, foram avaliados as melhores combinações sorvente/solvente (sílica gel, Florisil®, alumina neutra e polímeros de coordenação [Zn(BDC)(H2O)2]n, CuBTC, MIL-53/diclorometano, diclorometano:acetato de etila (1:1, v/v) e acetato de etila), na extração simultânea destes pesticidas. Dentre as combinações avaliadas, o sistema constituído de 0,5 g de C18 e 20 mL de diclorometano foi a mais eficiente, obtendo recuperações entre 85 e 127%, com desvio padrão relativo entre 4 e 15%, nos níveis de concentração 0,05; 0,1; 0,5 e 1,0 μg g-1. As linearidades foram acima de 0,9987 e os limites de detecção foram entre 0,02 e 0,07 μg g-1 e de quantificação, 0,05 e 0,1 μg g-1. Entre as fases poliméricas (CuBTC, MIL-53 e [Zn(BDC)(H2O)2]n), o [Zn(BDC)(H2O)2]n foi a mais eficiente na extração de pirimetanil (83%), ametrina (95%), diclofluanida (90%), tetraconazol (81%), flumetralina (74%) e cresoximmetílico (94%), sendo portanto uma alternativa viável a substituição do sorvente convencional C18.

Ces travaux consistent en l’étude selon trois axes de la chimie de coordination des ligands de type acyle-hydrazone, faisant suite à l’isolation d’un complexe binucléaire de manganèse (III) portant un tel ligand, et montrant un fort couplage ferromagnétique. Le développement de leur chimie de coordination avec des éléments de la première série de transition a permis la synthèse de plusieurs complexes binucléaires, permettant d’étudier la relation entre les structures moléculaires de ces systèmes, et leurs propriétés magnétiques. En parallèle, une série de polymères de coordination de métaux alcalins et alcalino-terreux portant des ligands acyle-hydrazone fonctionnalisés par un groupement sulfonate a été étudiée. Enfin, la synthèse de deux ligands dérivés d’un anthracène est présentée, celle-ci est accompagnée d’une étude de leurs propriétés de coordination. / This work consists in the study of the coordination chemistry of acyl-hydrazone ligands, following the discovery of a manganese (III) dinuclear complex showing a strong ferromagnetic coupling. The development of the acyl-hydrazone coordination to first-row transitional metals resulted in several dinuclear complexes allowing the study of the relationship between their structural and magnetic properties. In a second part the study of several coordination polymers of alkali and alkali-earth metals bearing acyl-hydrazone ligands functionalized with a sulfonate group is presented. Finally the synthesis of two anthracene-based ligands is presented along a study of their coordination properties.

La conception de matériaux capables de piéger sélectivement le CO2 revêt un enjeu majeur dans le développement de procédé de capture post-combustion pour de nombreux secteurs industriels. Nos travaux visent l'élaboration de nouveaux polymères de coordination de type MOF (“Metal-Organic Framework”) préparés par auto-assemblage de briques moléculaires polycarboxyliques avec des métaux de transition qui constituent les noeuds du réseau tridimensionnel. Ces matériaux hybrides microporeux présentent des propriétés d’adsorption du CO2 importantes. Notre approche a consisté à synthétiser des polymères de coordination dans le but d'accroître la capacité et la sélectivité d'adsorption du CO2 vis-à-vis d'autres gaz comme CO, CH4, N2 et O2 grâce à des interactions physiques impliquant le moment quadripolaire élevé du CO2 et le potentiel électrostatique existant dans les pores du matériau. Dans ce mémoire sont décrites les synthèses des différentes briques moléculaires organiques constituées de polyamines et de polyazamacrocycles Nfonctionnalisées par des terminaisons benzocarboxylate. Des matériaux homo- et hétéro- bimétalliques présentant des structures cristallines originales ont été obtenus à partir de briques moléculaires triazamacrocycliques N-fonctionnalisées par des terminaisons acides carboxyliques et différents cations métalliques (Zn2+, Co2+, Cd2+ et Ni2+). Les études de ces polymères de coordination poreux ont révélé leur capacité d’adsorption importante du CO2 avec une sélectivité remarquable dans les conditions normales de température et de pression. / The design of material able for CO2 capture is a major issue to achieve post-combustion capture process for many industries. Our work aims to develop new coordination polymer MOF (“Metal-Organic Framework”) prepared by self-assembling polycarboxylic linkers and transition metals. These microporous hybrids materials show important CO2 adsorption properties and are promising in the field of gas separation. The main topic of our work is to synthesise MOFs with high adsorption capacity and selectivity for CO2 over other gases (CO, CH4, N2 and O2). The gas-solid interactions are due to physical phenomena involving the high quadrupolar moment of CO2 and the electrostatic potential lying in the pore of the material. In this manuscript, the synthesis of various organic linkers incorporating N-functionalised polyamines and polyazamacrocycles with benzocarboxylate functions is described. Homo- and hetero- bimetallic materials with original tridimensional structure were obtained from a N-functionalised triazamacrocyclic linker and different metal cations (Zn2+, Co2+, Cd2+ and Ni2+). Studies of porous coordination polymers have shown high CO2 adsorption capacity with a remarkable selectivity in the ambient temperature and pressure conditions.

L’objet de cette étude est d’utiliser la technique des micelles inverses pour synthétiser des nanoparticules à transition de spin, de taille et de forme contrôlées afin d’en permettre l’utilisation en électronique moléculaire. Dans la première partie, nous avons déterminé les paramètres de synthèse influençant la taille et la forme des particules d’un complexe à transition de spin à fort potentiel d’application. Dans un deuxième temps, nous avons utilisé ces paramètres sur trois autres complexes afin de comprendre la relation entre les paramètres de la synthèse et la morphologie des particules. Les nanoparticules ainsi synthétisées constituent la base d’une discussion sur l’existence d’un lien entre la taille/forme des particules et les propriétés de transition de spin. Enfin, la dernière partie de ce travail est consacrée à l’utilisation de ces matériaux en électronique moléculaire, et l’observation des propriétés de photoconductivité et photovoltaïque à l’échelle des nanoparticules. / The aim of this project is to use the reverse micelles technique to synthesize spin crossover (SCO) nanoparticles with controlled size and shape in order to use them in molecular electronic applications. In the first part, we have determined the synthesis parameters that influence the particles size and shape of an attractive spin crossover complex, due to his potential application. In a second time, we used the determined parameters on three other SCO complexes to generalize the relationship between the synthesis parameters and the particles morphology. All the as-prepared nanoparticles are the basis of a discussion about the existence of a link between the size and/or shape of the particles and the SCO properties. The last part of this work is dedicated to the utilization of this materials in molecular electronic, and the observation of photovoltaic and photoconductive properties at the nanoparticles scale.

Ein zentraler Nachteil der meisten Koordinationspolymere ist, dass sie elektrische Isolatoren sind. In dieser Arbeit wurden konjugierte Koordinationspolymere auf ihre Leitfähigkeit untersucht, die eine Rhodium-Paddle-Wheel-Struktur besitzen. Die Beschichtung auf einer funktionalisierten Oberfläche im Vorfeld der C-AFM-Messung wurde mittels eines selbstgebauten Dip-Coaters realisiert. Koordinationspolymere, die das [Rh2(ac)4]-Paddle-Wheel enthalten, sind unabhängig von den untersuchten Linkern Isolatoren. Werden die Acetatliganden mit drei oder vier Acetamidatliganden ausgetauscht, so ist das entstandene Koordinationspolymer leitfähig. Temperaturabhängige C-AFM-Messungen ergeben eine für hohe Feldstärken konstante Aktivierungsenergie, die je nach Koordinationspolymer zwischen 0,3 eV und 0,7 eV beträgt. Anhand der Ergebnisse wurde gezeigt, dass der Ladungstransport durch einen Hopping Mechanismus dominiert wird. C-AFM ist eine aussagekräftige Methode zur Charakterisierung leitfähiger Koordinationspolymere auf der Oberfläche.

No description available.

[pt] O magnetismo molecular tem despertado muito interesse devido a possível aplicação em componentes de materiais eletrônicos. Esses tipos de materiais podem ser criados através de compostos de coordenação, como os polímeros de coordenação, que têm a capacidade de serem materiais multifuncionais. Neste trabalho foram sintetizados 11 compostos inéditos, divididos em dois sistemas que diferem conforme a composição dos materiais. O primeiro sistema utilizou a mistura do ligante policarboxilato BTB e do ligante N-doador como phen e dmdpy para avaliar a influência desses ligantes auxiliares na estrutura e propriedades dos complexos. A família que utiliza fen como ligante auxiliar gerou dois polímeros de coordenação isomorfos 1D com Cu(2+) e Co(2+) como íons metálicos. Medições de EPR para o polímero Cu(2+) não mostraram quase nenhuma interação magnética entre íons metálicos. Devido ao fato de ambos os CPs serem isomorfos, as mesmas pequenas interações magnéticas eram esperadas para o Co(2+) CP, o que é um indicativo do possível comportamento da molécula magnética devido ao forte ZFS de cobalto. A medição da suscetibilidade magnética fora de fase mostrou o comportamento do nanoímã. Um tempo de relaxação de tensão no ponto de escoamento = 5,52(4) × 10(-7)s e barreira de energia de 12,1(3) K foram determinados para este complexo. A mudança do ligante doador de N de phen para dmdpy resultou em um dímero de Cu(2+)pentacoordenado, porém, como o ligante divergente para ambas as famílias era o mesmo, a pequena interação entre os íons cobre(II) foi obtida, como evidenciado por EPR e magnetização medições. O segundo sistema apresenta íons Ln(3+) com ácido cumarínico-3-carboxílico como ligante orgânico, onde duas famílias diferentes foram obtidas alterando a proporção de íons Ln e ligante. A primeira família 1D CP foi obtida com ambos os componentes na mesma proporção. Estudos magnetocalóricos foram realizados para o Gd(3+) e o valor de entropia magnética máxima obtido foi menor que o valor esperado. Para os CPs Tb(3+) e Dy(3+) apresentaram potencial como nanoímãs devido ao sinal obtido nas medidas magnéticas dinâmicas. Foram realizados estudos fotoluminescentes para CPs Eu(3+) e Tb(3+), onde foram estimados tempos de vida de emissão de 0,30 ± 0,05 ms e 0,13 ± 0,05 ms. A segunda família obtida apresentou proporção de Ln(3+) e 3-HCCA de 1:3, e resultou em um polímero de coordenação 1D, onde a extensão da cadeia polimérica teve o mesmo mecanismo. Foram realizados estudos fotoluminescentes para CPs Eu(3+) e Tb(3+), onde foi observado um aumento no tempo de vida da emissão de 0,30 ± 0,05 ms para 0,45 ± 0,05 ms para o derivado Eu(3+) devido à remoção de uma molécula de H2O coordenada ao íon európio. Este trabalho resultou, até o momento desta dissertação, na publicação de dois artigos científicos, além de outro adicional que está em processo de review. / [en] Molecular magnetism has created a lot of interest due to its possible application in components of electronic materials. These types of materials can be created through coordination compounds such as coordination polymers, which have the capacity to be multifunctional materials. In this work, we synthesized a total of 11 new complexes organized in two systems that differ according to the composition of materials. The first system utilized the mixture of polycarboxylate ligand BTB and N-donor ligand such as phen and dmdpy to evaluate the influence of these auxiliary ligands in the complexes structure and properties. The family utilizing phen as auxiliary ligand generated two isomorph 1D coordination polymers with Cu(2+) and Co(2+) as metal ions. EPR measurements for Cu(2+) polymer showed almost no magnetic interactions between metal ions. Due to both CPs being isomorph, the same small magnetic interactions were expected for Co(2+) CP, which is an indicative of possible magnetic molecule behavior due to cobalt strong ZFS. Out-of-Phase magnetic susceptibility measurement showed the nanomagnet behavior. A relaxation time of yield point stress = 5.52(4) × 10(-7) s and energy barrier of 12.1(3) K were determined for this complex. The change of N-donor ligand from phen to dmdpy resulted in a pentacoordinated Cu(2+) dimer, however, since the divergent ligand for both families was the same, the small interaction between the copper(II) ions was obtained, as evidenced by EPR and magnetization measurements. The second system presents Ln(3+) ions with Coumarin-3-carboxylic acid as the organic ligand, where two different families were obtained by changing the proportion of Ln ions and ligand. First family 1D CP were obtained with both components with the same proportion. Magnetocaloric studies were conducted for the Gd(3+) and the obtained maximum magnetic entropy value was smaller than the expected value. For the Tb(3+) and Dy(3+) CPs displayed potential as nanomagnets due to the signal obtained in dynamic magnetic measurements. Photoluminescent studies for Eu(3+) and Tb(3+) CPs were conducted, where 0.30 ± 0.05 ms and 0.13 0.05 ms emission lifetime was estimated. The second family obtained had a Ln(3+) and 3-HCCA proportion of 1:3, and resulted in a 1D coordination polymer, where the extension of the polymeric chain had the same mechanism. Photoluminescent studies for Eu(3+) and Tb(3+) CPs were conducted, where an increase in the emission lifetime from 0.30 mais ou menos 0.05 ms to 0.45 0.05 ms for Eu(3+) derivate was observed due to the removal of one H2O molecule coordinated to the europium ion. This work resulted, at the time of this dissertation, in the publication of two scientific papers, as well as a submitted paper that is currently under review.