Nous visons dans ce travail de thèse à développer une méthodologie de fonctionnalisation par chimie click des silices hybrides synthétisées par voie sol-gel. La réaction click de cycloaddition azoture-alcyne catalysée au cuivre (CuAAC) offre une tolérance exceptionnelle pour les fonctions organiques en plus de conversions très élevées. Dans cette optique, nous avons mis en œuvre en premier lieu des matériaux clickables à base d'organosilice pure (organosilice à mésoporosité périodique (PMO) et silsesquioxanes pontés (BS)) qui ont permis une conversion quasi-quantitative de greffage par CuAAC. Nous avons ensuite utilisé cette particularité pour contrôler les propriétés de surface des BS en modifiant leur caractère hydrophile/lipophile. Dans le second axe de travail, nous nous sommes intéressés à l'apport de la chimie click pour la préparation de nanoparticules mésoporeuses de silice multifonctionnelles, dites mécanisées, pour des systèmes à délivrance contrôlée de principes actifs. / The present work aims to develop a trustful methodology of functionalization for hybrid silica materials made by the sol-gel process using the copper-catalyzed alkyne-azide cycloaddition (CuAAC)Click reaction. This transformation can be highly useful in materials science thanks to its high conversions and the excellent functional group tolerance. In this prospect, we have synthesized fully clickable bridged silisesquioxanes and periodic mesoporous organosilica that show high extents of click grafting. CuAAC was then used for tailoring the surface of bridged silsesquioxane and fine-tuning the hydrophilic/lipophilic balance. Finally, the click reaction was used as an efficient way to obtain multiply functionalized mesoporous silica nanoparticles in order to make nanomachines for controlled delivery of cargo molecules.

A study has been undertaken with the aim of preparing appropriately functionalised polyhedral oligomeric silsesquioxane (POSS) compounds to be used in ambient-cure chemistry. Numerous epoxy-functionalised compounds have been designed and synthesised and these materials have been characterised in order to determine their chemical structure. These compounds have also been incorporated into existing polymerisation reactions to test whether these materials could be used in the protective coatings industry. A glycidyl-functionalised POSS compound was prepared and reacted with a series of amines to produce ambient-cured polymers which could be used in the coatings industry. There were also a series of experiments undertaken on these polymers to identify the processes at work and to test how they compare to industry standards. As a direct comparator to this work, another set of results was obtained with a cyclic-siloxane material incorporated into the systems in place of the POSS. A linear analogue was also tested. The reactions proved to be a success and an appropriate data-set was yielded. During the synthesis of POSS precursors there are a series of residual materials produced. These materials have also been studied in this project. It was anticipated that these would behave in a similar way to the POSS compounds however the same functionality was never achieved as had been with the POSS. Ambient-cured polymers have also been targeted from a basic hydride-functionalised POSS compound and a polybutadiene system. The appropriate reactions unfortunately never took place as anticipated but there were a series of tests undertaken to identify the processes at work. A study has also been undertaken using near-I.R. to track the curing reactions. From this data, the extent of cure could be studied and the make-up of the reaction could be investigated in more detail.

Orientador: Devaney Ribeiro do Carmo / Resumo: Neste trabalho, novos nanocompósitos híbridos a base de silsesquioxano e nitroprussiato de cobalto e zinco foram preparados, seguindo dois métodos de síntese. Os materiais preparados foram caracterizados empregando diferentes técnicas: Espectroscopia na Região do Infravermelho por transformada de Fourier (FTIR), Espectroscopia Raman, Espectroscopia de Reflectância Difusa UV/Vis, Ressonância Magnética Nuclear (RMN), Difração de Raios-X (DRX), Microscopia Eletrônica de Varredura (MEV), Espectroscopia de Energia Dispersiva de Raios-X (EDX), Microscopia Eletrônica de Transmissão (MET) e Análise Termogravimétrica (TGA). Após a obtenção dos nanocompósitos com complexos metálicos de nitroprussiato (ACCoN e ACZnN), realizou-se um estudo sistemático sobre o comportamento voltamétrico desses materiais, empregando técnicas eletroquímicas, tais como: Voltametria Cíclica (VC) e Voltametria de Pulso Diferencial (VPD), utilizando eletrodos de pasta de grafite. O eletrodo de pasta de grafite contendo ACCoN mostrou-se sensível a concentrações de hidrazina e isoniazida. Já o eletrodo de pasta de grafite contendo ACZnN foi aplicado na detecção de N-acetilcisteína e isoniazida com sucesso. Após os testes de eletro-oxidação catalítica dessas substâncias, realizou-se uma investigação da influência dos principais interferentes, de forma que a interferência observada não se mostrou significativa. Avaliou-se também a recuperação destas substâncias a partir de amostras de água da torneira e urina sint... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: In this work, new nanocomposites based on silsesquioxane and cobalt and zinc nitroprusside were prepared, following two synthetic methods. The prepared materials were characterized by different techniques: Fourier Transform Infrared Spectroscopy (FTIR), Raman Spectroscopy, UV-Vis Diffuse Reflectance Spectroscopy, Nuclear Magnetic Resonance (NMR), X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM), Energy Dispersive X-ray spectroscopy (EDX), Transmission Electron Microscopy (TEM), Thermogravimetric Analysis (TGA). After obtaining the nanocomposites with metallic nitroprusside complexes, it was carried out a systematic study on the voltammetric behavior of these materials, using electrochemical techniques, such as: Cyclic Voltametry (CV) and Differential Pulse Voltammetry (DPV), using graphite paste electrodes. The graphite paste electrode containing ACCoN was sensitive to concentrations of hydrazine and isoniazid. The graphite paste electrode containing ACZnN was applied to the detection of N-acetylcysteine and isoniazid, with success. After catalytic electrooxidation tests of these substances, it was investigated the influence of the main interferents, so that the noticed interferences were not significant. Also, it was evaluated the recovery of these substances from samples of tap water and synthetic urine. By this way, the binuclear hybrid nanocomposites formed (ACCoN and ACZnN) are potential candidates for the construction of electrochemical sensors in the hydrazi... (Complete abstract click electronic access below) / Doutor

Orientador: Devaney Ribeiro do Carmo / Resumo: A detecção, especiação e remoção de contaminantes orgânicos e inorgânicos é uma das maiores preocupações ambientais atualmente. Assim, a busca por tecnologias eficientes envolvendo materiais de baixo custo para a resolução de tal problema tem aumentado, e se tornou de extrema importância. Dentro deste contexto, o presente trabalho atuou na produção de um novo material nanoestruturado bioinorgânico híbrido com grandes potencialidades na área de nanotecnologia. O objetivo principal consistiu em modificar quimicamente a levedura Saccharomyces cerevisiae com silsesquioxanos cúbicos. Após devidas modificações, o material preparado (LevS) bem como seus precursores, foram caracterizados por técnicas espectroscópicas tais como infravermelho (FTIR) e microscopia eletrônica de varredura (MEV). O material hibrido formado (LevS) foi aplicado como biossorvente de chumbo (Pb) e níquel (Ni), obtendo-se uma capacidade máxima de sorção de 248 mg g-1 e 64,6 mg g-1, respectivamente, e porcentagem de sorção chegando a 100% para 500 ppm de Pb2+ em 250mLg-1 de razão líquido/sólido em pH 4, e 77,7% para 100 ppm de Ni2+ em 100 mLg-1 de razão líquido/sólido em pH 6. Adicionalmente com intuito de avaliar a toxidade neuronal dos metais em questão, foram efetuados testes de toxicidade em fatias de hipocampo de ratos que comprovaram que, uma vez submetidos à concentrações de 1 e 3 μM (0,2 e 0,6 ppm) Pb2+ e 10 e 30 μM (0,5 e 1,5 ppm) de Ni2+, as alterações neuronais causadas são irreversíveis. O material ... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The detection, speciation and organic and inorganic contaminants removal is one of the biggest environmental concerns today. Thus, the search for efficient technologies involving low-cost materials for solving such a problem has increased, and became extremely important. Within this context, the present work was focused in the production of a new nanostructured hybrid material bioinorganic with great potential in the area of nanotechnology. The main objective was chemically modify the yeast Saccharomyces cerevisiae with cubic silsesquioxane. After appropriate modifications, the prepared material (LevS) as well as its precursors was characterized by spectroscopic techniques such as infrared (FTIR), scanning electron microscopy (SEM), energy dispersive x-ray (EDS) and Diffuse Reflectance UV/Vis. The hybrid material formed (LevS) was applied as biosorbent of lead (Pb) and nickel (Ni), with a maximum capacity of sorption of 248 mg g-1 and 64.6 mg g-1, respectively, and percentage of reaching 100% sorption to 500 ppm of Pb2+ on 250 cm3 g-1 liquid/solid ratio and 4 pH, and 77.7% to 100 ppm of Ni2+ on 100 cm3 g-1 liquid/solid ratio at pH 6. In addition, in order to evaluate the neuronal toxicity of the metals in question, toxicity tests were performed on hippocampal slices of mice that proved that, once submitted to concentrations of 1 and 3 μM (0.2 and 0.6 ppm) Pb2+ and 10 and 30 μM (0.5 and 1.5 ppm) of Ni2+, neuronal changes caused are irreversible. The hybrid material was also te... (Complete abstract click electronic access below) / Doutor

Regiomeric mixture of HMe2Si(CH2)3(i-Bu)6Si7O9(OH)3 (6), containing a Si-H group in one of the ligands of the silsesquioxane, was tethered onto a vinyl terminated hyperbranched poly(siloxysilane) polymer via a hydrosilation reaction to generate extremely active catalysts, P1-8 and c-P1-8. The synthesis of 6, in good yield, was accomplished via hydrosilation of CH2=CHCH2(i-Bu)7Si8O12 (1) to generate ClMe2Si(CH2)3(i-Bu)7Si8O12 (3) followed by the reduction of 3 with LiAlH4 to afford HMe2Si(CH2)3(i-Bu)7Si8O12 (4) where the base-catalyzed excision of one framework silicon was employed to generate a regiomeric mixture of 6. [Ti(NMe2){Et3Si(CH2)3(i-Bu)6Si7O12}] (7), [Ti(NMe2){HMe2Si(CH2)3(i-Bu)6Si7O12}] (8), [Ti(NMe2){(i-C4H9)7Si7O12}] (9) and [Ti(NMe2){(c-C6H11)7Si7O12}] (10) were synthesized via protonolysis of Ti(NMe2)4 with one equivalent of the trisilanol precursor in order to determine if the presence of isomers would be intrinsically different as compared to the uniformly substituted catalysts. Isomers 8 and 9, demonstrated lower activity as compared to the uniformly substituted catalysts 9 and 10, however the isomers still exhibited extremely high catalytic activity for the epoxidation of 1-octene using tert-butyl hydroperoxide (TBHP) relative to titanium catalysts used in industry. Additionally, 9, 10, P1-8 and c-P1-8 were very selective catalysts for the epoxidation of various olefins such as terminal (1-octene), cyclic (cyclohexene or 1-methylcyclohexene), and more demanding olefins (limonene or α-pinene) employing TBHP as the oxidant. Furthermore, P1-8 and c-P1-8 were recyclable with minimal loss of titanium however the catalysts could also be repaired if a loss in activity was observed. Preliminary epoxidation reactions employing P1-8 and c-P1-8 along with hydrogen peroxide (H2O2) as the oxidant were also explored using different solvents. P1-8 degraded quickly due to the hydrolysis of the titanium from the large amount of water present in the reaction mixture however c-P1-8 showed activity for the epoxidation of cyclohexene. Finally, regiomeric mixture of Ti(NMe2)(HS(CH2)3)(i-C4H9)6Si7O12) (13), was tethered onto gold nanoparticles for the conversion of propene to propylene oxide using molecular hydrogen and oxygen. While the catalysts showed low activity under our reaction conditions, numerous improvements can be investigated in order to improve upon the catalysts.

Orientador: Devaney Ribeiro do Carmo / Banca: Newton Luiz Dias Filho / Banca: Regina Massako Takeuchi / Resumo: O presente trabalho apresenta a preparação de um silsesquioxano nanoestruturado, o cloropropilsilsesquioxano (S) que foi organofuncionalizado com os seguintes agentes modificadores: 4-amino-3-hidrazinico-5-mercapto-1,2,4-triazol (Purpald®) e o 4-amino-5-4(piridil)-4H-1,2,4-triazol-3-tiol (APTT), os materiais obtidos dessa funcionalização foram descritos como SP e SA, respectivamente. Os materiais SP e SA foram caracterizados por diversas técnicas espectroscópicas: Espectroscopia na região do infravermelho (FT-IR), Ressonância magnética nuclear 29Si e 13C no estado sólido (RMN), Difração de Raios- X (DRX), Espectroscopia de Energia Dispersiva de Raios X (EDX), Termogravimetria e Análise Térmica Diferencial (TG - DTA). Após a devida caracterização, realizaram-se estudos de adsorção de íons metálicos (Cu2+, Cd2+ e Ni2+) nos sítios ativos do SA, porém, curiosamente não se observou a mesma capacidade de sorção pelo SP. Diferentes meios foram estudados no processo de adsorção dos íons metálicos supracitados: aquoso, etanólico 99% e etanólico 42%, determinando-se o tempo de equilíbrio de adsorção, que para ambos os meios e metais esse tempo máximo foi em média 35 min. Determinado o tempo de equilíbrio de adsorção dos íons metálicos em cada sistema, determinou-se a capacidade específica de sorção (Nfmax) através de isotermas de adsorção. Para o Cu2+, os valores de Nf foram: meio aquoso (3,09 × 10-4 mol g-1), etanólico 42% (1,03 × 10-4 mol g-1) e etanólico 99% (1,86 × 10-4 mol g-1), com concentrações de íons Cu2+ variando de 1,74 a 29,64 mol L-1. Os valores encontrados para o Ni2+ foram: em meio aquoso (2,11 × 10-4 mol g-1), etanólico 42% (0,97 × 10-4 mol g-1) e etanólico 99% (1,05 × 10-4 mol g-1), com concentrações de íons Ni2+ variando de 2,25 a 33,18 mol L-1. Para os íons cádmio não foram... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: This work presents the preparation of a nanostructured silsesquioxane, the cloropropilsilsesquioxano (S) that was organofunctionalised with the following modifying agents: 4-amino-3-hydrazino 5 - mercapto 1,2,4 triazole (Purpald ®) and 4- amino-5-4 (pyridyl)-4H-1,2,4-triazole-3-thiol (APTT), the materials obtained of the functionalization were described as SP and SA, respectively. The materials SA and SP were characterized by various spectroscopic techniques such as spectroscopy in the region of infrared (FTIR), nuclear magnetic resonance 29Si and 13C solid-state (NMR), X-ray diffraction (XRD), Energy Dispersive Spectroscopy Rays (EDS), Thermogravimetry and Differential Thermal Analysis (TG - DTA). After proper characterization, were carried studies on adsorption of metallic ions such as Cu2+, Ni2+ and Cd2+ in the active sites of SA, but curiously did not observe the same sorption capacity of the SP. Different methods were studied in the adsorption of metal ions above: aqueous, 99% ethanolic and 42% ethanolic, determining the adsorption equilibrium time, which for both means and metals the maximum time averaged 35 min. After determining the adsorption equilibrium time of metal ions in each system, we determined the specific sorption capacity (Nfmax) through adsorption isotherms. For Cu2+, the values of Nf were: aqueous solution (3.09 × 10-4 mol g-1), 42% ethanolic (1.03 × 10-4 mol g-1) and 99% ethanolic (1.86 × 10-4 mol g-1), with Cu2 + ion concentrations ranging from 1.74 to 29.64 mol L-1. The values obtained for the Ni2+ were: aqueous solution (2.11 × 10-4 mol g-1), 42% ethanolic (0.97 × 10-4 mol g-1) and 99% ethanolic (1.05 × 10-4 mol g-1), with Ni2 + ion concentrations ranging from 2.25 to 33.18 mol L-1. For the cadmium ions were not observed saturation of adsorption sites in the concentration range studied, not getting the maximum... (Summary complete electronic access click below) / Mestre

Made available in DSpace on 2014-06-11T19:25:33Z (GMT). No. of bitstreams: 0 Previous issue date: 2006-08-30Bitstream added on 2014-06-13T18:29:01Z : No. of bitstreams: 1 rangel_sa_me_ilha.pdf: 1557624 bytes, checksum: 38398c09b8ff17af075a211027a27833 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Polímeros epoxídicos são um dos mais importantes tipos de polímeros termorrígidos, extensivamente usados como adesivos e estruturas. Em reações epoxídicas são convertidos em um sistema termorrígido pela ação de agentes de cura. Tais reações químicas provocam uma mudança no estado físico do material, partindo de um líquido viscoso para um gel e se transformando em um material vitrificado. Os termorrígidos apresentam excelentes propriedades, tais como: alta tensão de ruptura e módulo de Young, fácil processamento, resistência térmica e química, e estabilidade dimensional. Entretanto, são quebradiços e possuem baixa resistência a propagação de trincas. Para superar estes inconvenientes, muitos tipos de compósitos de polímero com reforço foram desenvolvidos, em que as resinas epoxídicas são reforçadas com agentes modificadores, tais como enchimentos, oligômeros poliédricos de silsesquioxanos, dendrímeros, etc. Oligômeros poliédricos de silsesquioxanos (POSS), (RSiO1.5)n com n = 4, 6, 8, 10..., são nanoplataformas organo-funcionalizadas com 1 a 8 grupos reativos ou não reativos (R) ligados aos oito vértices possíveis do silsesquioxano cúbico. POSS octaédrico (n = 8) são os membros mais importantes desta família. No POSS, o núcleo cúbico de silicato é uma partícula rígida com 0,53 nm de diâmetro e um raio esférico de 1-3 nm, incluindo unidades orgânicas periféricas. Neste trabalho, um oligômero poliédrico de silsesquioxano contendo oito grupos epoxídicos por molécula (OG) foi incorporado ao sistema epoxídica DGEBA/DETA, como objetivo de avaliar a influência de um modificador reativo suas propriedades mecânicas e térmicas. Por meio de ensaios mecânicos foi observado um decréscimo de 30-50% na resistência à fratura (K1C)... / Epoxy resins are one of the most important kind of thermosetting polymers, extensively used for adhesives and structural applications. On cure, linear epoxy resins are undergoes in a thermoset system for the action of cure agents. Such chemical reactions cause a change into the physical state, from a viscous liquid to a gel and eventually to a vitrified material. They show various desirable properties such as high tensile strength and modulus, easy processing, good thermal and chemical resistance and dimensional stability, but they are brittle and have poor resistance to crack propagation. To overcome these drawbacks, many types of polymer-filler composites have been developed, in which the epoxy resins are reinforced with modifying agents, such as fillers, polyhedral oligosilsesquioxanes, dendrimers, etc. Polyhedral oligomeric silsesquioxanes (POSS), (RSiO1.5)n with n = 4, 6, 8, 10 ...., are organofunctional nanoplatforms with 1 to 8 reactive or nonreactive groups (R) connected to the eight possible vertexes of cubic silsesquioxanes. POSS Octahedral (n = 8) are the most important members of this family. In the POSS, the cubic core silica is a hard particle rigid with 0.53 nm diameter and a spherical radius of 1-3 nm including peripheral organic units. In this work, a polyhedral oligomeric silsesquioxanes containing eight epoxy groups per molecule (OG) was incorporated to an epoxy system of DGEBA/DETA thermosetting polymers in order to investigate the influence of a reactive modifier over the their mechanical and thermal properties. Through the mechanical tests an decrease of about 30-50% was observed in the fracture toughness (K1C) without or with a very soft decreasing in the module of Young (E)... (Complete abstract, click electronic address below)

Made available in DSpace on 2014-06-11T19:32:10Z (GMT). No. of bitstreams: 0 Previous issue date: 2009-04-03Bitstream added on 2014-06-13T19:21:28Z : No. of bitstreams: 1 costa_rm_dr_bauru.pdf: 1098183 bytes, checksum: 25def17b0af877f4604042281b271f05 (MD5) / Neste trabalho nós reportamos a síntese, caracterização, adsorção e propriedades dos materiais nomeados de octa[3-(2-amino-1,3,4-tiadiazol)propil]silsesquioxano (ATD-SSQ), octa[3-(3-amino-1,2,4-triazol)propil]silsesquioxano (ATZ-SSQ), octa[3-94-amino-2-mercaptopirimidina)propil]silsesquioxano (4-MCP-SSQ), octa[3-(2-mercaptopirimidina)propil]silsesquioxano (MCP-SSQ) e octa[3-(tioureia)propil]silsesquioxano (TIOU-SSQ). As isotermas de adsorção do M'X IND. 2'(M = Cu(II),Ni(II); X ='Cl POT.-', 'Br POT.-') para ATD-SSQ, ATZ-SSQ, 4MCP-SSQ e TIOU-SSQ. Foram estudadas em solução aquosa e etanólica a 25ºC. As adsorções em solução de etanol foram mais altas que em solução aquosa devido a alta polaridade da água, com maior força de solvatação do soluto e sítios básicos na superfície. As isotermas de adsorção de Cu'Cl IND. 2', Cu'Br IND. 2' e Ni'Cl IND. 2', em soluções etanólica e aquosa foram executadas usando o método da batelada. As condições de equilíbrio foram observadas em um tempo abaixo de 20min para todos os nanomateriais. Os resultados obtidos em experimentos de fluxo usando o método de coluna, demonstraram uma recuperação de 100% dos íons metálicos adsorvidos em uma coluna empacotada com 2g de nanomaterial, usando mL de HCl 1 mol 'L POT. -1' como solução eluente. A sorção-desorção dos íons metálicos possibilitou o desenvolvimento de um método para pré-concentração e determinação de íons metálicos a nível traço em etanol comercial, usado como combustível para automóveis. Os valores determinados pelo método recomendado para as usinas 1, 2 e 3 indicaram uma quantidade de cobre de 51,60 e 78 mg 'L POT. -1', e de ferro de 2, 15, e 3 mg 'L POT. -1', respectivamente. O ATZ-SSQ também foi testado para a determinação (em fluxo usando a técnica de coluna) dos íons metálicos presentes em águas naturais. Estes valores obtidos foram... / In this work we report on the synthesis, characterization, adsorption and properties of the nanomaterials named octa[3-(2-amino-1,3,4-tiadiazole)propyl]silsesquioxane (ATD-SSQ), octakis[3-(3-amino-1,2,4-triazole)propyl]silsesquioxane (ATZ-SSQ), octakis[3-94-amino-2-mercaptopirimidine)propyl]silsesquioxane (4-MCP-SSQ), octakis[3-(2-mercaptopirimidina)propyl]silsesquioxano (MCP-SSQ) e octakis[3-(thioureia)propyl]silsesquioxane (TIOU-SSQ). The isotherms of M'X IND. 2'(M = Cu(II),Ni(II); X ='Cl POT.-', 'Br POT.-') para ATD-SSQ, ATZ-SSQ, 4MCP-SSQ e TIOU-SSQ. Were studied in ethanol and aqueous solutions at 298K. Adsorptions from ethanol solutions were higher than those from aqueous solutions due to the higher polarity of water, which can more strongly solvate the solute and the basic sites on the surface. The adsorption isotherms for Cu'Cl IND. 2', Cu'Br IND. 2' and Ni'Cl IND. 2' from ethanol and aqueous solutions were performed by using the batchwise method. The equilibrium condition is reached at time lower than 20 min for all nanomaterials, ATD-SSQ, ATZ-SSQ, 4MCP-SSQ, MCP-SSQ and TIOU-SSQ. The results obtained in the flow using a column experiments, showed a recovery of the 100% of the metal ions adsorbed in a column packed with 2g of the nanomaterial, using 5 mL of 1.0 mol 'L POT. -1' HCl solution as eluent. The sorption-desorption of the metal ions made possible the development of a method for preconcentration and determination of metal ions at trace level in commercial ethanol, used as fuel for car engines. The values determined by recommended method for plants 1, 2 and 3 indicated an amount of copper of 51, 60, and 78 'L POT. -1', and of iron of 2, 15, and 3mg 'L POT. -1', resoectuvely. The ATZ-SSQ was also tested for the determination (in flow using a column technique) of the metal ions present in natural waters. These values are very close... (Complete abstract click electronic access below)

付記する学位プログラム名: 充実した健康長寿社会を築く総合医療開発リーダー育成プログラム / 京都大学 / 新制・課程博士 / 博士(工学) / 甲第23227号 / 工博第4871号 / 新制||工||1760(附属図書館) / 京都大学大学院工学研究科高分子化学専攻 / (主査)教授 田中 一生, 教授 秋吉 一成, 教授 古賀 毅 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

The structures of endohedral complexes of the polyhedral oligomeric silsesquioxane (POSS) cage molecule (HSiO 3/2) 12, with both D 2d and D 6h starting cage symmetries, containing the atomic or ionic species: Li 0, Li +, Li -, Na 0, Na +, Na -, K 0, K +, K -, F -, Cl -, Br -, He, Ne, Ar were optimized by density functional theory using B3LYP and the 6-311G(d,p) and 6-311 ++G(2d,2p) basis sets. The exohedral Li +, Na +, K +, K -, F -, Cl -, Br -, He, Ne, Ar complexes, were also optimized. The properties of these complexes depend on the nature of the species encapsulated in, or bound to, the (HSiO 3/2) 12 cage. Noble gas (He, Ne and Ar) encapsulation in (HSiO 3/2) 12 has almost no effect on the cage geometry. Alkali metal cation encapsulation, in contrast, exhibits attractive interactions with cage oxygen atoms, leading to cage shrinkage. Halide ion encapsulation expands the cage. The endohedral X@(HSiO 3/2) 12 (X = Li +, Na +, K +, F -, Cl -, Br -, He and Ne) complexes form exothermically from the isolated species. The very low ionization potentials of endohedral Li 0, Na 0, K 0 complexes suggest that they behave like "superalkalis". Several endohedral complexes with small guests appear to be viable synthetic targets. The D 2d symmetry of the empty cage was the minimum energy structure in accord with experiment. An exohedral fluoride penetrates the D 6h cage to form the endohedral complex without a barrier.