La première partie de ce mémoire concerne l’étude en solution de systèmes à base de POMset de cations organiques de polarité/taille variables. Ainsi, l’étude des interactions entre unanion Keplerate noté {Mo132} et une large série de cations organiques (composée d’ions alkylammonium AA) a nécessité la mise en place d’une méthodologie spécifique utilisant la RMNDOSY de 1H. La méthode s’est révélée particulièrement efficace et a permis non seulement demettre clairement en évidence l’existence d’interactions anion-cation fortes mais aussil’extraction des constantes d’association à partir d’un traitement quantitatif des données. Cetteétude révèle que le facteur qui domine le processus d’association anion-cation résulte d’un« effet hydrophobe » directement lié au caractère apolaire du cation organique et polaire dusolvant. Les constantes de stabilité sont en accord avec des interactions plutôt fortes. ParParailleurs, une expérience spécifique a permis de titrer les 20 pores présents à la surface de l’ionKeplérate, montrant ainsi la spécificité du processus d’association.La seconde partie de ce mémoire concerne la conception de matériaux à base de Képlerate enjouant sur la nature des cations imidazolium qui lui sont associés. Les phases solides ont étécaractérisées par spectrométrie infrarouge, analyse élémentaire, EDX et analysethermogravimétrique. Ces études montrent que dans certaines conditions, ces systèmes seaffichent un comportement type cristal liquide.La troisième partie s’intéresse spécifiquement aux interactions ionique et/ou van der Waals àl’origine de phénomènes de structuration. L’anion cyclique[Na2K2{Mo4O4S4(H2O)3(OH)2}2(P8W48O184)]32- ( noted 1) a été isolé à l’état solide sous laforme de sels de DODA (dioctadécyl-diméthyl-ammonium) ou d’imidazolium. L’analysestructurale de ces phases par RMN MAS de 1H, 13C et 31P montre sans ambigüitél’organisation des chaines alkyles. Ces résultats croisés avec la microscopie optique polarisée,l’analyse thermique différentielle et la diffraction des rayons X aux petits angles montrentclairement la formation de phases mésomorphes lamellaires dont l’espacement estdirectement lié à la longueur des chaines alkyles. / Herein, we report the use of 1H DOSY NMR methodology to track the interaction between aninorganic multireceptor capsule, referring to the well-defined spherical Keplerate-type{Mo132} ion and a series of organic cation (including tetraalklylammonium). The obtainedresults reveal a strong dependence of the self-diffusion coefficient of the cationic guestsbalancing from the solvated to the plugging situations. Quantitative analysis of the data basedon two-site exchange regime, involving the 20 independent {Mo9O9} receptors of the capsule,allowed determining the stability constants associated to the plugging process of the pores.Surprisingly, the affinity of the capsule for a series of cationic guests increases continuouslywith its apolar character. Such observations evidence that the major factor dictating selectivityin the trapping process is mainly the so-called “hydrophobic effect”.Further investigation focused on the design of Keplerate-based materials where theammonium cations was replaced by imidazolium cations. The obtained materials werecharacterized in the solid state by FT-IR, TGA and elemental analysis. These materials exhibitliquid crystalline phase as evidenced by polarized optical microscopy and DSC, however,folding of the alkyl chain prohibit the formation of well organized mesophase. Finally, thisstrategy was extended to cyclic [Na2K2{Mo4O4S4(H2O)3(OH)2}2(P8W48O184)]32- which wasisolated as DODA or imidazolium salt. Solid state NMR evidence the well organization of thesolid. The obtained materials exhibit smectic A liquid crystalline phase and packed ashexagonal lamellar arrangement in the solid state.

A birrefringência fotoinduzida e a formação de grades de relevo vêm sendo extensivamente investigadas em filmes de azopolímeros, obtidos por diversas técnicas de fabricação. Embora para azopolímeros amorfos já haja modelos bem estabelecidos tanto para explicar a dinâmica de fotoindução da birrefringência quanto para o transporte de massa que leva à formação de grades de relevo, o mesmo não ocorre para os azopolímeros líquido-cristalinos. Numa tentativa de contribuir para dirimir dúvidas da literatura, nesta dissertação foi sintetizado um azopolímero com diferentes massas molares, depois empregado em medidas de armazenamento óptico e fotoinscrição de grades de relevo. A síntese dos polímeros foi feita a partir do 4,4-difenilmetano-diisocianato (MDI) e de um azomonômero, sintetizado em três etapas: síntese do azocorante, incorporação do segmento flexível e funcionalização do monômero. Os materiais foram caracterizados por espectroscopia ultravioleta-visível (UV-Vis), espectroscopia infravermelha (FTIR) e ressonância magnética nuclear de hidrogênio (1H-RMN). A massa molecular dos polímeros (Mn e Mw) foi determinada por cromatografia de exclusão de tamanha (HPSEC). Através de calorimetria diferencial exploratória (DSC), microscopia óptica polarizada e difração de raios X foram comprovadas as propriedades líquido-cristalinas do azomonômero e dos polímeros. A transição da fase anisotrópica para a isotrópica ocorreu em aproximadamente 79oC no monômero e 84oC para os polímeros. Filmes de Langmuir estáveis foram obtidos para os polímeros na interface ar-água, propiciando a transferência para substratos sólidos na forma de filmes Langmuir-Blodgett (LB). Esses filmes foram usados para armazenamento óptico, sendo que a birrefringência fotoinduzida foi mais alta do que em filmes cast, provavelmente devido à melhor organização do filme LB. Grades de relevo foram inscritas nos dois tipos de filme usando um laser de baixa intensidade, ao contrário do que encontra na literatura, em que grades só são formadas se lasers de altas intensidades são empregados. Embora a amplitude das grades seja pequena e o processo de fotoinscrição ainda precise ser otimizado, este resultado abre novas perspectivas de emprego de azopolímeros líquido-cristalinos. / Photoinduced birefringence and surface-relief gratings (SRGs) have been extensively investigated in azopolymer films obtained with various film-fabrication methods. Even though well-established models exist for amorphous azopolymers which explain the dynamics of photoinduced birefringence and mass transport leading to SRGs, the same is not true for liquid-crystalline azopolymers. In an attempt to try and resolve controversies in the literature, in this work we synthesized an azopolymer with two different molar masses, which were then employed in optical storage and photoinscription of SRGs. The synthesis was performed with 4,4-diphenylmethane-diisocyanate (MDI) and an azomonomer obtained in a 3-step procedure: synthesis of the azodye, incorporation of the flexible segment and functionalization of the monomer. The materials were characterized by ultraviolet-visible spectroscopy (UV-Vis), infrared spectroscopy (FTIR) and proton nuclear magnetic resonance (1H-NMR). The molar mass of the polymers was determined by high performance size exclusion chromatography (HPSEC). The liquid-crystalline properties of the azomonomer and azopolymers were confirmed via differential scanning calorimetry (DSC), polarized optical microscopy and X-ray diffraction, with a isotropic-liquid crystal phase transition occurring at ca 79oC and 84oC for the monomer and polymers, respectively. Stable Langmuir films made with the azopolymers could be formed at the air-water interface, which were transferred onto solid substrates in the form of Langmuir-Blodgett (LB) films. These LB films could be used in optical storage experiments, with the photoinduced birefringence being higher than in cast films of the same azopolymers, probably due to the better organization of the nanostructured LB films. SRGs could be photoinscribed on both types of film with a low-intensity laser beam, in contrast to the reports in the literature, according to which SRGs can only be inscribed on liquid-crystalline azopolymer samples if high laser intensities are used. Though the SRG amplitude was small and the photoinscription process still needs to be optimized, this finding may open the way for a host of new applications of liquid-crystalline azopolymers.

A birrefringência fotoinduzida e a formação de grades de relevo vêm sendo extensivamente investigadas em filmes de azopolímeros, obtidos por diversas técnicas de fabricação. Embora para azopolímeros amorfos já haja modelos bem estabelecidos tanto para explicar a dinâmica de fotoindução da birrefringência quanto para o transporte de massa que leva à formação de grades de relevo, o mesmo não ocorre para os azopolímeros líquido-cristalinos. Numa tentativa de contribuir para dirimir dúvidas da literatura, nesta dissertação foi sintetizado um azopolímero com diferentes massas molares, depois empregado em medidas de armazenamento óptico e fotoinscrição de grades de relevo. A síntese dos polímeros foi feita a partir do 4,4-difenilmetano-diisocianato (MDI) e de um azomonômero, sintetizado em três etapas: síntese do azocorante, incorporação do segmento flexível e funcionalização do monômero. Os materiais foram caracterizados por espectroscopia ultravioleta-visível (UV-Vis), espectroscopia infravermelha (FTIR) e ressonância magnética nuclear de hidrogênio (1H-RMN). A massa molecular dos polímeros (Mn e Mw) foi determinada por cromatografia de exclusão de tamanha (HPSEC). Através de calorimetria diferencial exploratória (DSC), microscopia óptica polarizada e difração de raios X foram comprovadas as propriedades líquido-cristalinas do azomonômero e dos polímeros. A transição da fase anisotrópica para a isotrópica ocorreu em aproximadamente 79oC no monômero e 84oC para os polímeros. Filmes de Langmuir estáveis foram obtidos para os polímeros na interface ar-água, propiciando a transferência para substratos sólidos na forma de filmes Langmuir-Blodgett (LB). Esses filmes foram usados para armazenamento óptico, sendo que a birrefringência fotoinduzida foi mais alta do que em filmes cast, provavelmente devido à melhor organização do filme LB. Grades de relevo foram inscritas nos dois tipos de filme usando um laser de baixa intensidade, ao contrário do que encontra na literatura, em que grades só são formadas se lasers de altas intensidades são empregados. Embora a amplitude das grades seja pequena e o processo de fotoinscrição ainda precise ser otimizado, este resultado abre novas perspectivas de emprego de azopolímeros líquido-cristalinos. / Photoinduced birefringence and surface-relief gratings (SRGs) have been extensively investigated in azopolymer films obtained with various film-fabrication methods. Even though well-established models exist for amorphous azopolymers which explain the dynamics of photoinduced birefringence and mass transport leading to SRGs, the same is not true for liquid-crystalline azopolymers. In an attempt to try and resolve controversies in the literature, in this work we synthesized an azopolymer with two different molar masses, which were then employed in optical storage and photoinscription of SRGs. The synthesis was performed with 4,4-diphenylmethane-diisocyanate (MDI) and an azomonomer obtained in a 3-step procedure: synthesis of the azodye, incorporation of the flexible segment and functionalization of the monomer. The materials were characterized by ultraviolet-visible spectroscopy (UV-Vis), infrared spectroscopy (FTIR) and proton nuclear magnetic resonance (1H-NMR). The molar mass of the polymers was determined by high performance size exclusion chromatography (HPSEC). The liquid-crystalline properties of the azomonomer and azopolymers were confirmed via differential scanning calorimetry (DSC), polarized optical microscopy and X-ray diffraction, with a isotropic-liquid crystal phase transition occurring at ca 79oC and 84oC for the monomer and polymers, respectively. Stable Langmuir films made with the azopolymers could be formed at the air-water interface, which were transferred onto solid substrates in the form of Langmuir-Blodgett (LB) films. These LB films could be used in optical storage experiments, with the photoinduced birefringence being higher than in cast films of the same azopolymers, probably due to the better organization of the nanostructured LB films. SRGs could be photoinscribed on both types of film with a low-intensity laser beam, in contrast to the reports in the literature, according to which SRGs can only be inscribed on liquid-crystalline azopolymer samples if high laser intensities are used. Though the SRG amplitude was small and the photoinscription process still needs to be optimized, this finding may open the way for a host of new applications of liquid-crystalline azopolymers.