published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

No description available.

Neste trabalho, materiais fotocrômicos foram preparados pela imobilização de um heteropolioxometalato do tipo Keggin, fosfotungstato [PW12O40]3- (HPW) em uma matriz híbrida do tipo Ormosil (do inglês Organically Modified Silicates). Estudou-se o impacto da adição dos cátions divalentes Zn2+, Mg2+, Ca2+, Sr2+ e Ba2+ sobre as propriedades dos filmes de Ormosil-Fosfotungstato. Os materiais foram preparados pelo método sol-gel e depositados na forma de filmes em diferentes substratos pela técnica de dip-coating. A formação da rede híbrida de organosilicato e a presença do [PW12O40]3- com sua estrutura de Keggin intacta nos materiais foram comprovadas pelas técnicas de espectroscopia vibracional (FTIR e Raman). Os difratogramas de raios-X das amostras de xerogéis demonstram que os materiais apresentam caráter semicristalino, sendo que um pico na região de 2θ<10° sugere a formação de unidades discretas de octasilsesquioxanos e/ou lamelas de silicato. Estudos de microscopia eletrônica de transmissão revelaram que a adição dos cátions durante a síntese induz a precipitação de nano-aglomerados constituídos de HPW e dos cátions dopantes. A análise do XANES na borda K do Zn sugere que os cátions dopantes Zn2+ estão associados aos heteropoliânions em aglomerados do sal [Zn(OH2)6]x/2Hx-3PW12O40. A imobilização destes aglomerados na rede de organosilicato durante a deposição dos filmes acarreta na preparação de filmes com maior quantidade incorporada de fosfotungstato, como demonstrado pela análise de XRF. A formação dos aglomerados é favorecida pela presença dos cátions maiores, sendo que a adição do Ba2+, que possui maior raio iônico dentre os cátions aqui estudados, permite a incorporação de quase sete vezes mais fosfotungstatp no filme de Ormosil. Essa maior incorporação dea espécie fotoativa nos filmes híbridos se reflete no aumento resposta fotocrômica dos filmes dopados de 35% (amostra dopada com Mg2+) até 685% (amostra dopada com Ba2+). Assim, a adição dos cátions, sobretudo daqueles com maior raio iônico, durante a síntese sol-gel do nanocompósito Ormosil-fosfotungstato representa uma estratégia simples e bastante reprodutível para a preparação de filmes com propriedades fotocrômicas aprimoradas. A elevada resposta fotocrômica dos filmes dopados os torna bons candidatos a serem aplicados como dosímetros colorimétricos da radiação UV. / In this study photohromic materials wer prepared by the entrapment of the Keggin heteropoyoxometalate phosphoungstate [PW12O40]3 (HPW) in a Ormosil (Organically Modified Silicates) hybrid matrix. We evaluated the impact of the addition of the divalent cations Zn2+, Mg2+, Ca2+, Sr2+ and Ba2+ on the properties of Ormosil-phosphotungstate films. The materials were prepared by sol-gel route and deposited as thin films on different substrates by dip coating method. The formation of the hybrid organosilicate network and the presence of the Keggin heteropolianion [PW12O40]3- were confirmed by FTIR and Raman vibrational spectroscopies. The x-ray diffractograms of the xerogels samples indicated that the materials present semi-crystalline behavior. A broad diffraction peak in the 2θ<10° region pointsto the possible formation octasilsesquioxane discrete units and/or silicate lamellae. Transmission electron microscopy studies revealed that the cations addition during the sol-gel synthesis induces the precipitation of nano-agglomerates composed of HPW and the doping cations. Zn K-edge XANES analysis suggests that the Zn2+ doping cations are associated to the heteropolianions forming [Zn(OH2)6]x/2Hx-3PW12O40 salt agglomerates. The entrapment of these agglomerates in the organosilicate network during dip-coating deposition results in the preparation of films with enhanced incorporation of phosphotungstate as demonstrated by XRF analysis. Ba2+ doping enhances in almost seven times the amount of incorporated phosphotungstate. This behavior is explained by the fact that as the solubility of polyoxometalate salts greatly decreases with the increase counter cation size, the formation of the agglomerates is favored in the presence of the larger cations (Sr2+ and Ba2+). The enhanced incorporation of the photoactive specie reflects on the phtochromic response of the doped hybrud films, wich increases in the range of 35% (Mg2+ doped sample) to 685% (Ba2+ doped sample). Therefore, the addition of the cations during sol-gel synthesis of the Ormosil-phosphotungstate nanocomposite represents a simple and reproducible strategy for the preparation of films with enhanced photochromic properties. These highly photochromic hybrid films are promising candidates for the design of practical UV-sensing devices and dosimeters.

Submitted by LUCAS BRAGA DE MELLO null (lucaomello12@gmail.com) on 2016-10-10T23:06:13Z No. of bitstreams: 1 DISSERTAÇÃO MESTRADO Lucas Prata PDF.pdf: 1870553 bytes, checksum: 6998aa62034574fa649ce2ba13deebdf (MD5) / Rejected by Ana Paula Grisoto (grisotoana@reitoria.unesp.br), reason: Solicitamos que realize uma nova submissão seguindo a orientação abaixo: O arquivo submetido está sem a ficha catalográfica. O arquivo submetido não contém a folha de aprovação. A versão submetida por você é considerada a versão final da dissertação/tese, portanto não poderá ocorrer qualquer alteração em seu conteúdo após a aprovação. Corrija esta informação e realize uma nova submissão com o arquivo correto. Agradecemos a compreensão. on 2016-10-11T16:02:02Z (GMT) / Submitted by LUCAS BRAGA DE MELLO null (lucaomello12@gmail.com) on 2016-10-11T23:16:56Z No. of bitstreams: 1 DISSERTAÇÃO MESTRADO Lucas Mello Versão Final PDF.pdf: 3076697 bytes, checksum: adb1c134f37b4f27c08705c14999bfeb (MD5) / Approved for entry into archive by Juliano Benedito Ferreira (julianoferreira@reitoria.unesp.br) on 2016-10-17T17:32:16Z (GMT) No. of bitstreams: 1 mello_lc_me_rcla.pdf: 3076697 bytes, checksum: adb1c134f37b4f27c08705c14999bfeb (MD5) / Made available in DSpace on 2016-10-17T17:32:16Z (GMT). No. of bitstreams: 1 mello_lc_me_rcla.pdf: 3076697 bytes, checksum: adb1c134f37b4f27c08705c14999bfeb (MD5) Previous issue date: 2016-10-06 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / O processo Sol-Gel tem permido preparar materiais vítreos ou vítro-cerâmicos com novas composições com alto grau de pureza, homogêneos, materiais híbridos orgânicos e inorgânicos (OIHM) e até materiais impossíveis de serem preparados por processos convencionais. Um dos melhores sistemas para obtenção dos OIHM de sílica (ORMOSIL – Silicato Organicamente Modificado) é a reação combinada com alcoóxidos de Silício como o TEOS (Tetraetilortosilicato) e alcoóxidos funcionalizados como o GPTS (3-Glicidoxipropil-trimetoxisilano). A Prata, é aplicada em diversas áreas como por exemplo, em pinturas a base de Prata (utilizados para circuitos impressos), em filmes fotográficos, películas de vidros dentre várias outras aplicações. Dois efeitos encontrados quando uma amostra GTD-Ag (Amostra com a dopagem de AgNO3), irradiada por uma lâmpada UV e tratada a temperatura (acima de 80 °C), são os efeitos fotocrômicos e termocrômicos. Para o efeito fotocrômico, a irradiação por lâmpada UV, produz partículas de prata oxidadas (Ag+) que transformam-se em partículas de prata reduzidas (Ago), ocorrendo-se assim, o escurecimento dos filmes (redução). O clareamento das amostras GTD-Ag (oxidação), foi obtido através de um agente oxidante, o H2O2. Para observar o efeito termocrômico, as amostras GTD-Ag, são tratadas em forno convencional em temperaturas de 80 °C à 550 °C em atmosferas de N2 e ambiente. No tratamento térmico em atmosfera de N2, foi possível observar o escurecimento (redução) da amostra, a partir da temperatura de 80 °C, e em tratamento térmico à atmosfera ambiente, observamos um clareamento da amostra (oxidação), a partir da temperatura de 200 °C. Utilizando a técnica de análise térmica diferencial (DTA), foi possível verificar a óxido-redução da amostra GTD-Ag, quando tratada em atmosfera ambiente, em temperaturas superiores a 150 °C. Comportamento semelhante é observado para as amostras GTD (Amostra sem dopagem de AgNO3), em temperaturas acima de 200 °C, ocorrendo um efeito conhecido por pirólise, que no nosso caso é a degradação do grupo epóxi. / The sol-gel process has allowed prepare vitreous or vitro-ceramic materials with novel compositions with high purity, homogeneous, organic and inorganic hybrid materials (OIHM) and impossible materials to be prepared by conventional methods. One of the better systems for obtaining OIHM silica (ORMOSIL - Silicate Organically Modified), is the combined reaction of silicon alkoxides such as TEOS (Tetraethylorthosilicate), and functionalised alkoxides such as GPTS (3- Glycidoxypropyl-trimethoxysilane). The Silver is applied in various areas such as Silver paintings (used for printed circuits) on photographic films, glass films among many other applications. Two effects found when a GTD-Ag sample (Sample with AgNO3 doping) irradiated by a UV lamp and treated at temperatures (above 80 °C), are photochromic and thermochromic effects. For the photochromic effect, the UV irradiation lamp produces oxidized silver particles (Ag+) which becomes reduced particles silver (Agº), occurring to thereby darkening of the films (reduction). The samples of the bleaching GTD-Ag (oxidation) were obtained by an oxidizing agent H2O2. To observe the thermochromic effect, the GTD-Ag samples are treated in a conventional oven at temperatures of 80 °C to 550 °C in N2 atmosphere and ambient. In the heat treatment in N 2 atmosphere, was observed to darkening (reduction) of the sample from the 80 °C temperature and treatments to the ambient atmosphere, we observed a whitening of the sample (oxidation) at low temperature 200 °C. Using the differential thermal analysis (DTA), we found the redox sample GTD-Ag, when treated in atmosphere ambient at temperatures above 150 °C. Similar behavior is observed for the GTD samples (Sample undoped AgNO3) at temperatures above 200 °C, occurring an effect known by pyrolysis which in our case is the degradation of the epoxy group.

Le développement des nouvelles technologies, de l'informatique et d'internet ces dernières décennies s'est accompagné d'une demande croissante de supports de stockage de l'information. En particulier, le stockage optique de données. Les supports conventionnels (Cd-Rom, Blue-ray…), basés sur un stockage en surface du disque, ont atteint aujourd'hui leurs limites. Une nouvelle technologie en cours de développement, basée sur un stockage de données en trois dimensions, est une alternative prometteuse pour supplanter les supports conventionnels. Les matériaux doivent intégrer des entités aux propriétés photochromes (commutateur moléculaire) et d'absorption multi-photonique démontrées. Au cours de cette thèse, nous avons envisagé la synthèse de molécules fonctionnelles qui présenteraient ces deux caractéristiques. Dans un premier temps, nous nous sommes intéressés à la synthèse et à l'étude comparative de complexes homo et hétéroleptiques de ruthénium présentant une certaine potentialité pour l'absorption à deux photons. Nous avons montré que ces systèmes étaient très actifs et qu'ils permettaient d'accueillir une entité photochrome sans perte des propriétés bi-photoniques. Nous avons par la suite étudié les propriétés en photochromisme de complexes de ruthénium tris-bipyridine originaux comprenant un motif azobenzène. La complexation au métal bouleverse profondément le photochromisme de l'azobenzène avec des caractéristiques cinétiques notablement différentes de celles des ligands. Enfin, nous avons étudié les propriétés de complexes hybrides composés de ligands pour l'absorption à deux photons et d'autres pour le photochromisme, ces composés sont actifs dans ces deux domaines. Nous discutons finalement du potentiel du comportement optique de films composés de ces complexes. Nous avons procédé à des essais préliminaires de modulation du signal SHG sur ces films. Nous souhaitons optimiser toutes les composantes du processus afin de déterminer le potentiel de ces composés en stockage optique de données. / The development of new technologies , computer and internet in recent decades has been accompanied by an increasing demand for media storage information. In particular , the optical data storage .Conventional media ( CD-ROM , Blu-ray ... ) based on a storage disk surface, have now reached their limits. A new technology being developed , based on a data storage in three dimensions, is a promising alternative to replace conventional materials. Materials must include entities for photochromic properties (molecular switch) and multi- photon absorption demonstrated. In this thesis , we considered the synthesis of functional molecules which present these two characteristics. As a first step , we are interested in the synthesis and comparative study of homo and heteroleptic ruthenium complex having a certain potential for two-photon absorption . We have shown that these systems were very active and they allowed to host a photochromic entity lossless bi- photonic properties. We then studied the properties of originals photochromic ruthenium tris- bipyridine containing an azobenzene motif. The metal complexing profoundly changes the photochromism of azobenzene with significantly different from those ligands kinetics . Finally, we studied the properties of hybrid complexes of ligands for the two-photon absorption and others to photochromism , these compounds are active in both areas. We finally discuss the potential of the optical behavior of compounds of these complex films. We conducted preliminary tests of the SHG signal modulation on these films. We want to maximize all components of the process to determine the potential of these compounds in optical data storage .

Des nanoparticules (NPs) organiques photochromes (par réaction de cyclisation/cycloréversion entre une forme ouverte et une forme fermée) de diaryléthènes (P1 et PF1) ont été fabriquées par photofragmentation laser. La caractérisation des tailles et des propriétés photophysiques ont été effectuées par microscopie et spectroscopie (absorption UV-visible, DLS, AFM, MEB). Pour P1, l'influence de la fluence du laser et de la température sur la taille des NPs a été démontrée. Egalement, la compétition entre le photochromisme et la photofragmentation a été mise à profit pour contrôler la photofragmentation laser par la réaction photochrome. Une exaltation du rendement quantique de la réaction de cycloréversion par l'absorption à deux photons successifs a été montrée en solution. Dans le cas des NPs, la présence d’un processus d'annihilation S1-S1 accentue cette exaltation. Concernant PF1, la dépendance en longueur d’onde d’excitation du rendement quantique de cycloréversion en solution a été démontrée et plusieurs conformations de la forme ouverte ont été identifiées. Les NPs de PF1 sont apparues comme un bon compromis entre la phase solide (fluorescente, non photochrome) et la solution (peu fluorescente, photochrome) : elles permettent une photocommutation efficace de la fluorescence. Une dépendance en taille des rendements quantiques de cyclisation/cycloréversion et des propriétés de fluorescence a été observée dans le cas des NPs. Le transfert d’énergie intermoléculaire au sein des NPs permet d’amplifier l’extinction de fluorescence lors de la réaction photochrome. Ces résultats apportent des perspectives dans le stockage d'informations numériques de haute densité. / Nanoparticles (NPs) of organic photochromic (cyclization/cycloreversion reaction between open and closed forms) materials (P1 and PF1) were prepared by the laser ablation method. Their size and their photophysical properties were investigated by microscopy and spectroscopy methods (UV-visible absorption, DLS, AFM, SEM). Regarding P1, the influence of the laser fluence and the temperature on the NPs size was evidenced. The competition between photochromism and ablation process was used to control the NPs formation by photochromism. An enhancement of the cycloreversion reaction occurred, via a stepwise two-photon absorption. In addition, in NPs, S1-S1 annihilation led to a further enhancement. Concerning PF1, a thorough study, involving quantum yields determination and DFT calculations was made. The cycloreversion quantum yield in solution shows an excitation wavelength dependence and several conformations of the open form were identified. NPs of PF1 were also prepared, and behave as a balanced trade-off between bulk (fluorescent, non photochromic) and solution (weakly fluorescent, photochromic): they allow an efficient photoswitching of the fluorescence. NPs size dependence of the cyclization/cycloreversion quantum yields and fluorescence properties was evidenced. The intermolecular energy transfer processes within the NPs enhances the fluorescence quenching during the photochromic reaction. These results are aimed to bring new perspectives results in the field of high-density digital information storage.

Nesse estudo procurou-se avaliar o impacto do aditivo dióxido de titânio, mistura anatase-rutila, no comportamento fotocrômico de nanocompósitos baseados em materiais híbridos do tipo silicatos orgânicos (Ormosis) contendo ácido fosfotúngstico, \'H IND.3\'PW IND.12\'O IND.40\'. O material híbrido foi obtido via processo sol-gel tendo sido caracterizado quanto à sua morfologia por Microscopia óptica e Microscopia Eletrônica de Varredura (MEV), que mostrou que os filmes em geral são pouco rugosos e homogêneos. Estudos de Espectroscopia Vibracional (Espectroscopia de Absorção na Região do Infravermelho e Raman) confirmaram a integridade do heteropoliânion fosfotungstato e a formação de uma rede tridimensional de silicatos, assim como, permitiram identificar a abertura do anel oxirano para formar um poli(óxido de etileno) ramificado, caracterizando a formação de um material híbrido classe II. A Espectroscopia de absorção na região do Ultra-violeta visível (UV-vis) ou espectroscopia eletrônica, além de confirmar a integridade química da espécie fosfotungstato, permitiu acompanhar a formação de heteropoliazuis mono- e duplamente reduzidos de maneira quantitativa. A cristalinidade dos materiais foi avaliada por Difração de raios-x (DRX) e mostrando que o sólido resultante é amorfo. Os estudos espectroscópicos permitiram inferir que a interação entre os polioxometalatos e as nanopartículas de \'TI\'O IND.2\' deve ser fraca, entretanto, estudos posteriores são necessários para confirmar isto. A adição de nanopartículas leva a um material mais sensível à radiação UV, entretanto, não há uma correlação linear entre massa de nanopartículas adicionada e variação de absorbância devido à irradiação. / In this study we evaluated the impact of the additive titanium dioxide, anatase-rutile mixture, Photochromic behavior of nanocomposite materials based on hybrid organic-type silicates (Ormosia) containing phosphotungstic acid, \'H IND.3\'PW IND.12\'O IND.40\'. The hybrid material was obtained via sol-gel process has been characterized for their morphology by optical microscopy and scanning electron microscopy (SEM), which showed that the films are often little rough and smooth. Studies of Vibrational Spectroscopy (Absorption Spectroscopy in the infrared and Raman) confirmed the integrity of phosphotungstic acid and the formation of a three-dimensional network of silicates, as well as the opening of the oxirane ring to form a poly (ethylene oxide) branched characterizing the formation of a hybrid class II material. The absorption spectroscopy in the region of Ultra-violet visible (UV-vis) to confirm the chemical integrity of phosphotungstate species, allowed us to track the formation of mono-and doubly heteropolyblues reduced quantitatively. The crystallinity of the materials was evaluated by x-ray diffraction (XRD) and showed us that the resulting solid is amorphous. The spectroscopic studies allowed us to infer that the interaction between polyoxometalates and \'TI\'O IND.2\' nanoparticles should be weak, however, further studies are needed to confirm this. The addition of nanoparticles leads to a material more sensitive to UV radiation, however, there is not a linear correlation between mass of nanoparticles added and absorbance variation due to irradiation.

The thesis is aimed to the study of spiropyrane behavior in polymeric matrix of poly(N-vinylkarbazole) (PVK) and poly[2-methoxy-5-(3´,7´-dimethyloctyloxy)-1,4-fenylenvinylene)] (MDMO-PPV). The photochromic transformation of spiropyrane to its isomeric merocyanine form (SPMC) was studied by absorption and emission spectroscopy. It was found, that photochromic reaction is markedly dependent on the environment. In the PVK polymer, which don’t absorb in the visible region, a high yield of photochromic reaction was achieved. Both, absorption and emission spectrums were observed for this system. From the measurement of time dependencies of the fotochromic reaction, the activation energy of the reverse reaction was determined. A different behavior, particularly in emissive spectrums, was found for the MDMO-PPV polymer doped with spiropyrane. Instead of formation of new band of merocyanine, decrease of the polymer fluorescence was observed. Subsequently, we studied the interaction between the polymeric matrix and the photochromic spiropyrane using fluorescence quenching method. On the basis of energy transfer theory, a critical radius of the fluorescence quenching sphere in solution and in solid was determined.

Les polyoxométallates (POMs) sont des oxydes moléculaires solubles dont la facilité de fonctionnalisation permet l’accès à un grand nombre de propriétés telles que la catalyse, le magnétisme, la biologie ou l’optique. Cette thèse est donc consacrée à la synthèse de POMs hybrides possédant des propriétés dans les domaines de la biologie et de l’optique. Dans un premier temps, de nouveaux composés hybrides moléculaires comportant des POMs et des entités organiques de type bisphosphonate (BP) ont été synthétisés. Une étude in vitro a révélé les excellentes propriétés anticancéreuses de ces nouveaux assemblages. L’un d’entre eux a également fait l’objet de tests in vivo.Dans un second temps, des POMs hybrides photoactifs constitués de deux types de molécules organiques photochromes ont été synthétisés. Des dérivés de spiropyrane (SP) et de spironaphtoxazine (SN) ont été greffés sur des POMs. Ces assemblages ont été analysés en électrochimie puis leurs propriétés fonctionnalisantlesatomesdiridium photochromes à l’état solide ont été étudiées. D’autre part, un photochrome inverse appelé « donor-acceptor Stenhouse adduct » (DASA) a été greffé pour la première fois sur un POM. Les propriétés optiques de ce complexe ont été modulées par la nature du contre-ion associé.Des assemblages ioniques entre différents POMs et un complexe d’iridium ont été synthétisés et caractérisés. Les propriétés optiques de l’entité phosphorescente ont été modulées à l’état solide par la nature du POM. Un de ces assemblages possèdent des propriétés de vapoluminescence pouvant trouver une application dans le domaine de la détection de composés organiques volatils.Enfin, d’autres POMs hybrides associant de façon covalente un POM Anderson et des dérivés organiques appelés tétrathiafulvalène (TTF) ont été synthétisés et caractérisés. Après avoir été analysés en électrochimie, leurs propriétés en optique non linéaire ont été étudiées. / Polyoxometalates (POMs) are a unique class of molecular oxides that can be easily functionalized, hence opening the door to different fields such as catalysis, magnetism, etc. This thesis is devoted to the synthesis of hybrid POMs having properties in biology or optics. Firstly, new molecular hybrids were formed using POMs and organic bioactive entities called bisphosphonates (BPs). An in vitro study revealed the excellent anticancerous properties of these assemblies. One of them has also been subject to in vivo studies.Secondly, photoactive hybrid POMs constituted of two different photochromic organic molecules have been synthesized. Spiropyran (SP) and spironaphtoxazine (SN) derivatives have been covalently grafted onto an Anderson-type POM. These assemblies have been analyzed in electrochemistry functionalizing then their photochromic properties at the solid state have been studied. A new class of reverse photochromic entity called « donor-acceptor Stenhouse adduct » (DASA) has been grafted for the first time onto a POM. This complex’s optical properties have been modulated by the nature of the associated counter-ion.Ionic assemblies between POMs and an iridium complex have been synthesized. The influence of the POM’s nature on the luminescent properties of the complex has been studied. One of these new assemblies possesses vapochromisme properties.Finally, three hybrid POMs have been obtained from the covalent grafting of a tetrathiafulvalene (TTF) derivative. After their electrochemical properties have been analyzed, their properties in non linear optics have been studied.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第19318号 / 工博第4115号 / 新制||工||1634(附属図書館) / 32320 / 京都大学大学院工学研究科合成・生物化学専攻 / (主査)教授 松田 建児, 教授 北川 進, 教授 杉野目 道紀 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM