Self-assembly of colloidal microparticles is one of the strategies for making characteristic patterns. These versatile self-assemblies provide a route to elevate the efficiency of an electronic device. Silsesquioxane particles with various functionalities were synthesized by a modified Stöber condensation method. This thesis describes the synthesis of benzylchloride silsesquioxanes, benzylchloride-amine silsesquioxanes and amine-functionalized silsesquioxane particles with multi-fluorescent tags. The size and morphology of the particles were controlled by varying the concentration of base and anhydrous ethanol (solvent). The size distribution of particles was controlled by adjusting the molar ratios of organotrialkoxy silane, base, and ethanol concentrations. Through selective post-functionalization with fused arenes of anthracene and rhodamine, multifluorescent particles were obtained. Morphologies and optical properties of particles were characterized by TEM, SEM, fluorescence optical microscopy, and absorption and fluorescence spectroscopies. The composition of silsesquioxanes was confirmed by FTIR, thermogravimetric analysis, and elemental analysis. A versatile technique was developed for the self-assembly of particles on different polymer substrates by changing the colloidal suspension concentration and the polymer substrate.

Abstract Layered inorganic-organic hybrid compounds have been widely studied as new potential sources of semiconductors and other optical devices. They simulate natural quantum well materials, where the inorganic part acts as semiconductors, separated by an organic part. This class of hybrid materials has no covalent bonds between the inorganic and organic parts; instead, weak hydrogen bonds and van der Waals forces bind and stabilise the overall structure. The inorganic part is made up of layers of corner-sharing metal halide octahedra, MX6, where the metal must be in a divalent state and the halides are Cl, Br or I. The 2-D layers extend infinitely in two directions and are separated themselves by layers of primary ammonium cations, with only one ammonium group at one end of the chain, [(R-NH3)2MX4], or two ammonium groups at either of the chain, [(H3N-R-NH3)MX4]. Due to its similarity to the cubic perovskite structure, this inorganic motif is referred to as "layered perovskite-type". Depending on the choice of the organic ammonium cation, the materials can display phase transitions and / or have optical and electronic properties. Various investigations of inorganic-organic hybrids have concentrated on the phase transitions of the hybrids of general formula [(CnH2n+1NH3)2MX4] and [(NH3CnH2nNH3)MX4] (n = 1-18; X = Cl, Br, I; M = Cu2+, Mn2+, Cd2+) to elucidate their mechanism. There are two types of displasive transitions, a minor one were small conformational changes within the alkylammonium chain occurs, and a major one, when the entire alkylammonium chain becomes disordered along its long axis. The interlayer spacing between the inorganic layers increases with temperature and during the major phase transition. The methods used to identify the temperatures and the enthalpies of the phase transitions are Differential Scanning Calorimetry (DSC); and Single Crystal X-ray Diffraction (SC-XRD) as well as Powder X-Ray Diffraction (P-XRD) to follow the structural changes. In contrast, only a few reports on investigations of the lead iodide hybrids, [(CnH2n+1NH3)2PbI4] were found in the literature, with only two single crystal structures previously reported. Due to the difficulty in growing good quality crystals, the previous studies on the lead iodide hybrids have been only researched using DSC and P-XRD. The phase transition behaviour has been found to show the same trends as the previous hybrids. The primary aim of this study was to follow the same phase transitions via SC-XRD, ideally single-crystal to single-crystal, and to determine the detailed structural changes with the hopes of elucidating their detailed phase transition mechanism. A secondary aim was to synthesize as many inorganic-organic hybrids as possible using a variety of primary ammonium cations to find different inorganic motifs apart from the layered perovskite-type. Other inorganic motifs can have purely corner-, edge or face-sharing octahedra or combinations thereof to give 2-D net-type networks or 1-D extended chains. The effect that the identity of the ammonium cation has on the type of inorganic motif and the effect on the detailed structural geometry within the inorganic motif are investigated. Examples of structural geometries within the layered perovskite-type inorganic motif that can differ from compound to compound are the relative positions of the inorganic and organic moieties; the N---H….X hydrogen bonding geometry between the halides and the ammonium group; and the relative positions of successive inorganic layers.

Various synthetic methods have been developed to produce metal nanostructures including copper and iron nanostructures. Modification of nanoparticle surface to enhance their characteristic properties through surface functionalization with organic ligands ranging from small molecules to polymeric materials including organic semiconducting polymers is a key interest in nanoscience. However, most of the synthetic methods developed in the past depend widely on non-aqueous solvents, toxic reducing agents, and high temperature and high-pressure conditions. Therefore, to produce metal nanostructures and their nanocomposites with a simpler and greener method is indeed necessary and desirable for their nano-scale applications. Hence the objective of this thesis work is to develop an environmentally friendly synthesis method to make welldefined copper and iron nanostructures on a large-scale. The size and shape-dependent optical properties, solid-state crystal packing, and morphologies of nanostructures have been evaluated with respect to various experimental parameters. Nanostructures of copper and iron were prepared by developing an aqueous phase chemical reduction method from copper(II) chloride and Fe(III) chloride hexahydrate upon reduction using a mild reducing agent, sodium borohydride, under an inert atmosphere at room temperature. Well-defined copper nanocubes with an average edge length of 100±35 nm and iron nanochains with an average chain length up to 1.70 μm were prepared. The effect of the molar ratios of each precursor to the reducing agent, reaction time, and addition rate of the reducing agent were also evaluated in order to develop an optimized synthesis method for synthesis of these nanostructures. UV-visible spectral traces and X-ray powder diffraction traces were obtained to confirm the successful preparation of both nanostructrues. The synthesis method developed here was further modified to make poly(3-hexylthiophene) coated iron nanocomposites by surface functionalization with poly(3-hexylthiophene) carboxylate anion. Since these nanostructrues and nanocomposites have the ability to disperse in both aqueous-based solvents and organic solvents, the synthesis method provides opportunities to apply these metal nanostructures on a variety of surfaces using solution based fabrication techniques such as spin coating and spray coating methods.

The work presented in this thesis is divided into two research areas. In part I, the synthesis and guest intercalation of inorganic-organic metal halide ammonium layered perovskites is discussed. Comparisons are made between the solid matrix before and after the intercalations, and all solids are characterized using thermogravimetric analysis (TGA) and powder X-ray diffraction (XRD). In part II, “templateree” hydrothermal synthesis of tin oxide spheres in the presence of different ortho-substituted anilines is discussed. The aim is to determine whether there are differences in the structures, shapes and surface morphology of the tin oxide spheres that correspond to the identity/shape of the ortho-substituent on the anilines. Solids were characterized by XRD, transmission electron microscopy (TEM) and scanning electron microscopy (SEM) techniques.

Developing new materials with desired properties is a vital component of emerging technologies. Functional hybrid compounds make an important class of advanced materials that let us synergistically utilize the key features of the organic and inorganic counterparts in a single composite, providing a very strong tool to develop new materials with ”engineered” properties. The research presented here, summarizes efforts in the development of facile and efficient methods for the fabrication of three- and two-dimensional inorganic-organic hybrids based on layered oxide perovskites. Microwave radiation was exploited to rapidly fabricate and modify new and known materials. Despite the extensive utilization of microwaves in organic syntheses as well as the fabrication of the inorganic solids, the work herein was among the first reported that used microwaves in topochemical modification of the layered oxide perovskites. Our group specifically was the first to perform rapid microwave-assisted reactions in all of the modification steps including proton exchange, grafting, intercalation, and exfoliation, which decreased the duration of multi-step modification procedures from weeks to only a few hours. Microwave-assisted grafting and intercalation reactions with n-alkyl alcohols and n-alkylamines, respectively, were successfully applied on double-layered Dion-Jacobson and Ruddlesden-Popper phases (HLaNb2O7, HPrNb2O7, and H2CaTa2O7), and with somewhat more limited reactivity, applied to triple-layered perovskites (HCa2Nb3O10 and H2La2Ti3O10). Performing neutron diffraction on n-propoxy-LaNb2O7, structure refinement of a layered hybrid oxide perovskite was then tried for the first time. Furthermore, two-dimensional hybrid oxides were efficiently prepared from HLnNb2O7 (Ln = La, Pr), HCa2Nb3O10, HCa2Nb2FeO9, and HLaCaNb2MnO10, employing facile microwave-assisted exfoliation and post-exfoliation surface-modification reactions for the first time. A variety of surface groups, saturated or unsaturated linear and cyclic organics, were successfully anchored onto these oxide nanosheets. Properties of various functionalized metal-oxide nanosheets, as well as the polymerization of some monomer-grafted nanosheets, were then investigated for the two-dimensional hybrid systems.

Submitted by Maike Costa (maiksebas@gmail.com) on 2017-06-06T14:13:28Z No. of bitstreams: 1 arquivototal.pdf: 5719464 bytes, checksum: d95ea796f3e4195aab70df7f60654647 (MD5) / Made available in DSpace on 2017-06-06T14:13:28Z (GMT). No. of bitstreams: 1 arquivototal.pdf: 5719464 bytes, checksum: d95ea796f3e4195aab70df7f60654647 (MD5) Previous issue date: 2017-02-09 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / Magadiite (Na2Si14O29.xH2O, x = 5-10) is an alkaline layered silicate with unknown structure and reacts through intercalation with simple organic species and polymer resulting inorganic-organic hybrids, which can be applied as adsorbents for pollutants, catalytic support, cationic exchanger and others. In this work, sodium magadiite was obtained by hydrothermal synthesis and used as support to ion exchange to origin the acid, potassium, calcium and magnesium forms. The acid magadiite interacted with aliphatic diaminas, NH2(CH2)nNH2 where n = 8, 9, 10 e 12, in ethanolic medium, by using conventional and microwave heatings. The exchanged solids were evaluated for the ability to remove ranitidine in aqueous medium where contact time and initial drug concentration parameters were investigated. In vitro release tests were performed for sodium magadiite/ranitidine hybrid. The solids were characterized by X-Ray diffratometry (XRD), infrared spectroscopy (FIRT), CHN elemental analysis, thermogravimetry (TG/DTG) and UV-Vis molecular absorption spectroscopy in solid state before and after interaction with the diamines and drug. Hybrid materials formed between H-magadiite and diamines showed basal spacings between 0.200 to 0.286 nm resulting from the intercalation of both diamines and solvent molecules in the layered material, where the intercalated amount depended of size of organic chain, nature of solvent, temperature and type of heating. The Na-, H-, K-, Ca- and Mg exchanged magadiites removed ranitidine from aqueous solution, and the maximum capacities were 92.34 and 81.47 mg g-1 for sodium and potassium, respectively. The released tests of ranitidine was pH-dependent and presented the maximum released quantities of 76.4% in 48 h at SGF and 43.3% and 46.4% in 56 h in both SIF and SBF. Na- and K-magadiites showed potential adsorbents and drug vehicle for ranitidine while the H-magadiite/diamines intercalated hybrids had new organophilic properties, which result in new properties to interact with new organic species in solution. / A magadeíta (Na2Si14O29.xH2O, x = 5-10) é um silicato lamelar alcalino de estrutura ainda desconhecida que interage por intercalação com espécies orgânicas simples ou polímeros, originando híbridos inorgânico-orgânicos destinados a mais diversas aplicações como adsorventes, suporte para catalisadores, trocador catiônico, entre outras. Neste trabalho, a magadeíta sódica foi obtida por síntese hidrotérmica convencional e por troca iônica originou as suas formas ácida, potássica, cálcica e magnésica. A magadeíta ácida interagiu com diaminas alifáticas, NH2(CH2)nNH2 com n = 8, 9, 10 e 12, em meio etanólico, utilizando aquecimento convencional e por micro-ondas. Os sólidos trocados foram avaliados quanto à capacidade de remoção de ranitidina em meio aquoso, onde os parâmetros de tempo de contato e concentração inicial do fármaco foram investigados. Os ensaios de liberação in vitro foram realizados para o sistema magadeíta sódica/ranitidina. Os sólidos foram caracterizados por difratometria de raios X (DRX), espectroscopia na região do infravermelho (IV), análise elementar de CHN, termogravimetria (TG/DTG) e espectroscopia de absorção molecular UV-Vis no estado sólido antes e após a interação com as diaminas e com o fármaco. Os materiais híbridos formados entre a H-magadeíta e as diaminas mostraram variações no espaçamento basal de 0,200 a 0,286 nm, resultantes da intercalação tanto das diaminas como das moléculas do solvente na matriz lamelar, onde a quantidade intercalada foi dependente do tamanho da cadeia orgânica, temperatura e fonte de aquecimento. A magadeíta em suas formas trocadas com Na-, H-, K-, Ca- e Mg adsorveram ranitidina em meio aquoso cujas capacidades máximas de sorção foram de 92,34 e 81,47 mg g-1 para as formas sódica e potássica, respectivamente. A interação da ranitidina com os sólidos por intercalação também foi confirmada por DRX, IV, CHN e UV-Vis do estado sólido. Os ensaios emissão da ranitidina mostraram que a quantidade liberada foi dependente do pH dos fluidos, apresentando máximos de liberação de 76,4% em 48 h no fluido SGF e de 43,3% e 46,4% em 56 h nos fluidos SIF e SBF, respectivamente. As Na- e K-magadeítas mostraram bons adsorventes e veículo para ranitidina, enquanto os híbridos de intercalação magadeíta ácida/diaminas tiveram novas propriedades organofílicas, o que permite aplicações futuras para interação com diferentes espécies orgânicas em solução.

Réalisé en cotutelle, sous la direction du Pr. Bernold Hasenknopf, à l'Institut Parisien de Chimie Moléculaire, Université Pierre et Marie Curie (Paris VI, France) et dans le cadre de l'Ecole Doctorale "Physique et Chimie des Matériaux" - Spécialité Chimie Inorganique (ED397). / Notre projet se situe dans le contexte actuel de recherche d’énergies « propres », qui permettraient d’assurer un développement durable. Nous nous sommes intéressés à l’édification de systèmes moléculaires bio-inspirés, capables de : (i) collecter efficacement l’énergie solaire, grâce au design d’assemblages supramoléculaires multi-nucléaires photoactifs ; (ii) transférer efficacement l’énergie accumulée jusqu’au catalyseur, lequel effectue les processus multiélectroniques nécessaires à la génération des combustibles. Notre choix s’est porté sur les systèmes hybrides covalents inorganiques-organiques, à base de polyoxométallates (POMs) photoactivés, dans le visible, par des complexes de métaux de transition. Dans un premier temps, nous avons étudié des chromophores dinucléaires de Ru(II) comprenant le motif électroattracteur 1,3,5-triazine, en raison de leurs capacités de transfert d’énergie et pour la prolongation du temps de vie de l’état excité du chromophore. Dans un deuxième temps, la nécessité d’établir une connexion covalente entre le complexe métallique et le POM nous a amené à faire le design de ligands polydentates ditopiques de type trialkoxo. Cette méthodologie, flexible sur le plan synthétique, nous a donné accès à une famille de POMs présentant des sites de coordination de denticité variable (de monodentate à tridentate), en vue d’accommoder divers cations métalliques. Nous avons ensuite étudié la complexation de divers métaux de transition sur ces nouveaux POMs. Les systèmes visés étaient soit des systèmes à transfert de charges photoinduits (complexation de Ru, de Re), soit des systèmes photocatalytiques (complexation de Re et Co) et/ou électrocatalytiques (complexation de Co). L’auto-assemblage des POMs, guidé par le mode de coordination du métal (tel Pd(II) ou Re(I)) et la géométrie de la brique constituante POM, a été également étudié, car il constitue un outil puissant dans l’assemblage de systèmes supramoléculaires multi-nucléaires photoactifs. Les systèmes visés sont destinés à servir de systèmes modèles dans l’édification de systèmes moléculaires à composants multiples et de matériaux hybrides multi-fonctionnels. / We are interested in the photocatalytic production of clean energy sources, such as H2, in order to ensure global sustainable development. We focused our attention on molecular bio-inspired systems, capable of : (i) efficient light harvesting, based on the careful design of multi-nuclear supramolecular photoactive units; (ii) efficient energy transfer to the catalyst, chosen for its ability to perform multi-electronic processes needed in fuels production. We chose inorganic-organic covalent hybrids, constituted of visible-photoactivated POMs by transition metal complexes. First, we designed and studied Ru(II) dinuclear complexes, based on the electrodeficient motif 1,3,5-triazine, for their energy transfer properties and extended excited-state lifetimes. Then, the covalent connection, to ensure between sub-units, compelled us to design new ditopic polydentate ligands. This flexible synthetic methodology gave access to a family of POMs presenting various types of coordination sites (from monodentate to tridentate), in order to allow complexation of different metals. Complexation studies on the new POMs were conducted and aimed at : (i) photoinduced charge transfer systems (complexation of Ru, and Re) ; (ii) photocatalytic (complexation of Re and Co) and/or electrocatalytic systems (complexation of Co). Metal-directed self-assembling of POMs (guided by Pd(II) or Re(I)) and the coordination geometry of the POMs building-block, has also been studied, as a tool in the building-up of electro- and photoactive supramolecular systems. The model systems studied will be used to design molecular multi-functional hybrid materials.

Le travail présenté dans cette thèse porte sur l’isolement de métabolites secondaires de trois invertébrés marins, ainsi que sur la synthèse de molécules hybrides, notamment à visée antifouling et inhibiteurs de kinases, inspirées des motifs naturels issus des familles dispacamides et 3-alkylpyridines. Les techniques spectroscopiques et les transformations chimiques ont été largement utilisées pour les déterminations structurales. Les nouveaux composés ont été évalués biologiquement.Le travail d’isolement sur le corail mou Sinularia vanderlandi a permis de mettre en évidence trois nouveaux composés de la famille de diterpènes norcembranoïdes, dont les configurations relatives ont été déterminées. Un lien chimique a également été établi entre les nouveaux composés isolés ainsi que ceux de la même famille décrits dans la litérature.Neuf nouvelles molécules ont été obtenues de l’éponge Pipestela candelabra, quatre phopholipides et cinq composés de la famille du jaspamide, les pipestelides A-C ainsi que les 5-hydropéroxy-jasplakinolides Ca et Cb. Des travaux d’hémisynthèse ont été réalisés à partir du jaspamide pour confirmer les structures des dérivés hydropéroxydés. Cette thèse contient également une étude partielle de l’éponge Stylissa carteri qui a mis a jour deux nouvelles benzosceptrines.Les travaux de synthèses ont eu pour but d’établir les voies d’accès à des dérivés l’obtention dispacamide / 3-alkylpyridine. Trois dérivés ont ainsi été synthétisés et les évaluations biologiques sont en cours, notamment pour les activités antifouling. Des aspects structuraux de ce type de dérivés ont été abordés par la synthèse d’autres dérivés. / The work described in this thesis deals with the isolation of new metabolites from marine invertebrates in one hand, and with the synthesis of antifouling and kinase inhibitors hybrid molecules inspired from dispacamide and 3-alkylpyridine scaffolds. Spectroscopic methods and chemical modifications were used for structural determination. The new compounds were biologically evaluated.Three new compounds of the norcembranoid diterpenes were isolated from the Soft Coral Sinularia vanderlandi. The relative configurations of these metabolites were determined and a chemical link was established between these diterpenes.The investigation of the marine Sponge Pipestela candelabra has conducted to the isolation of nine new metabolites, four phospholipids and five new jaspamide congeners including pipestelides A-C and 5-hydroperoxy-jasplakinolides Ca et Cb. Hemisynthesis were conducted from the jaspamide, together with spectroscopic analysis to confirm the structures of the peroxidated compounds.Two new derivatives of benzosceptrine were isolated from a partial study of the marine Sponge Stylissa carteri.The synthesis part of this work described the access to dispacamide / 3-alkylpyridine derivatives. Three hybrids were synthetized and biological evaluation are in progress, particularly for antifouling activities. Structural aspects were also studied by the synthesis of other derivatives

Notre projet se situe dans le contexte actuel de recherche d’énergies « propres », qui permettraient d’assurer un développement durable. Nous nous sommes intéressés à l’édification de systèmes moléculaires bio-inspirés, capables de : (i) collecter efficacement l’énergie solaire, grâce au design d’assemblages supramoléculaires multi-nucléaires photoactifs ; (ii) transférer efficacement l’énergie accumulée jusqu’au catalyseur, lequel effectue les processus multiélectroniques nécessaires à la génération des combustibles. Notre choix s’est porté sur les systèmes hybrides covalents inorganiques-organiques, à base de polyoxométallates (POMs) photoactivés, dans le visible, par des complexes de métaux de transition. Dans un premier temps, nous avons étudié des chromophores dinucléaires de Ru(II) comprenant le motif électroattracteur 1,3,5-triazine, en raison de leurs capacités de transfert d’énergie et pour la prolongation du temps de vie de l’état excité du chromophore. Dans un deuxième temps, la nécessité d’établir une connexion covalente entre le complexe métallique et le POM nous a amené à faire le design de ligands polydentates ditopiques de type trialkoxo. Cette méthodologie, flexible sur le plan synthétique, nous a donné accès à une famille de POMs présentant des sites de coordination de denticité variable (de monodentate à tridentate), en vue d’accommoder divers cations métalliques. Nous avons ensuite étudié la complexation de divers métaux de transition sur ces nouveaux POMs. Les systèmes visés étaient soit des systèmes à transfert de charges photoinduits (complexation de Ru, de Re), soit des systèmes photocatalytiques (complexation de Re et Co) et/ou électrocatalytiques (complexation de Co). L’auto-assemblage des POMs, guidé par le mode de coordination du métal (tel Pd(II) ou Re(I)) et la géométrie de la brique constituante POM, a été également étudié, car il constitue un outil puissant dans l’assemblage de systèmes supramoléculaires multi-nucléaires photoactifs. Les systèmes visés sont destinés à servir de systèmes modèles dans l’édification de systèmes moléculaires à composants multiples et de matériaux hybrides multi-fonctionnels. / We are interested in the photocatalytic production of clean energy sources, such as H2, in order to ensure global sustainable development. We focused our attention on molecular bio-inspired systems, capable of : (i) efficient light harvesting, based on the careful design of multi-nuclear supramolecular photoactive units; (ii) efficient energy transfer to the catalyst, chosen for its ability to perform multi-electronic processes needed in fuels production. We chose inorganic-organic covalent hybrids, constituted of visible-photoactivated POMs by transition metal complexes. First, we designed and studied Ru(II) dinuclear complexes, based on the electrodeficient motif 1,3,5-triazine, for their energy transfer properties and extended excited-state lifetimes. Then, the covalent connection, to ensure between sub-units, compelled us to design new ditopic polydentate ligands. This flexible synthetic methodology gave access to a family of POMs presenting various types of coordination sites (from monodentate to tridentate), in order to allow complexation of different metals. Complexation studies on the new POMs were conducted and aimed at : (i) photoinduced charge transfer systems (complexation of Ru, and Re) ; (ii) photocatalytic (complexation of Re and Co) and/or electrocatalytic systems (complexation of Co). Metal-directed self-assembling of POMs (guided by Pd(II) or Re(I)) and the coordination geometry of the POMs building-block, has also been studied, as a tool in the building-up of electro- and photoactive supramolecular systems. The model systems studied will be used to design molecular multi-functional hybrid materials. / Réalisé en cotutelle, sous la direction du Pr. Bernold Hasenknopf, à l'Institut Parisien de Chimie Moléculaire, Université Pierre et Marie Curie (Paris VI, France) et dans le cadre de l'Ecole Doctorale "Physique et Chimie des Matériaux" - Spécialité Chimie Inorganique (ED397).