Le travail de cette thèse de doctorat est axé sur le design, la synthèse et la caractérisation de systèmes moléculaires organiques et organométalliques luminescents dans le but de déclencher des processus de transfert photoinduit d’électron (PeT) ou d’énergie (EET) pour des applications dans les dispositifs optiques ou électroniques. Nous nous sommes d’abord intéressés aux molécules de type push-pull car elless’avèrent être des modèles intéressants pour l’étude du PeT. Nos systèmes sont construits autour de BτDIPY qui sert d’espaceur entre le donneur d’électron (julolidine ou triazatruxène) et l’accepteur d’électron (une unité dicyanovinyl). Les études en électrochimie et spectroscopie ont montrés un caractère à transfert de charge très prononcé. Entre autre nous avons synthétisé et étudié une série de ligands de type N^O (type base de Schiff) dérivés de la julolidine, une amine cyclique avec des propriétés électroniques très inattendues. Ces ligands, subissent des processus de transfert photoinduit de proton à l’état excité (ESIPT) et leurs spectres d’émission présentent une luminescence panchromatique. La compléxation desligands N^O au BF2 supprime l’ESIPT et augment les rendements quantiques de fluorescence. Les ligands derivés de la julolidine sont combinés avec d’autres unités chromophoriques i.e. Ir(III), Pt(II) afin de construire des systèmes multichromophoriques et stimuler des processus de EET entre les composants.Lors de ces travaux de thèse nous nous somme particulièrement intéressés aux systèmes moléculaires photocommutables dont l’unité centrale est un photochrome, le [1,3]oxazine. L’oxazine est combiné à un module moléculaire qui sert de donneur d’énergie et un module accepteur d’énergie choisie de façon optimale afin d’induire un transfert électronique d’énergie de manière contrôlé. / The present doctoral thesis work deals with the design, synthesis and characterization of organic and organometallic luminescent molecular frameworks for triggering Photoinduced electron Transfer (PeT) and Electronic Energy Transfer (EET) processes for applications in optical andelectronic devices. First, we turned toward the organic push-pull chromophores because they are useful model systems for studying the mechanism of PeT process. We synthesized new push-pull systems bearing a dicyanovinyl fragment as the electron-acceptor and a strong electron-donorsuch as julolidine and triazatruxene covalently linked through a BODIPY dye bridge. Electrochemical and photophysical studies showed a pronounced charge transfer character within the new push-pull systems. Furthermore, we synthesized and studied a series of chelating N^O-type ligands (Schiff base-type), based on the strong electron-donating julolidine motif, displaying ESIPT process. Their luminescence profiles exhibited panchromatic luminescence band covering the whole visible spectrum. Complexation of N^O-site with boron difluoride fragment suppressed the ESPIT process and highly increased the fluorescence quantum yield. The N^O-chelating ligands were combined with Pt(II) chromophore, B(III) and Ir(III) such as to obtainmultichromophoric frameworks. According to the photophysical studies, EET processes were observed within the multichromophoric systems. We successfully obtained a new florescent switching triad constructed around a photochromic core, [1,3]oxazine, which bears an energy-donor and an energy-acceptor module such as to directly control the EET process.

The topic of thesis is motivation of experienced employees toward to starting own business. The purpose is to identify the attitudes of respondents to leave their job and decide to start own business within push-pull theory. Research is carried out on the basis of questionnaire which is divided into three parts. Results of thesis will be suggestions for companies to reduce workers leaving the job depending on push factors.

O ambiente competitivo atual tem colocado pressão no processo de tomada de decisão no mundo corporativo. Os trade-offs das prioridades competitivas discutidos na elaboração da estratégia como custo, qualidade, serviço e flexibilidade já não são suficientes. Estes trade-offs, embora importantes no curto prazo, devem ser compatibilizados de modo que as empresas que tenham o melhor balanço entre eles devam ter resultado superior. Um dos trade-offs bastante discutido é o equilíbrio entre serviço e estoque. A percepção é que seja improvável alcançar excelência no serviço sem ter um considerável nível de estoque. Deste cenário nasce então o paradoxo do uso de sistemas MRP (Material Requirement Planning) versus sistemas JIT (Just in Time), ou melhor, sistemas empurrados versus puxados, já que a escolha por um ou outro sistema tem ligação íntima com a gestão de estoque. Se por um lado os sistemas MRP são largamente utilizados, via softwares ERP, por outro sistemas JIT têm trazido importantes melhorias nos resultados. Embora muitas empresas considerem a adoção exclusiva de um ou outro sistema, algumas delas têm adotado um processo híbrido com o objetivo de tirar o melhor de cada sistema e gerar assim desempenho superior. O objetivo deste trabalho é investigar como as empresas inseridas em mercados caracterizados pela concentração de demanda no final do mês (fenômeno conhecido como hockey-stick), e baixo acerto nas previsões de demanda, estão aplicando suas estratégias de planejamento de produção e seus ERP. Se por um lado a baixa acurácia nas previsões causa um problema na aplicação de estratégias empurradas de planejamento, pois requer um alto estoque de segurança associado, por outro a concentração de embarque dificulta a adoção de uma estratégia puramente puxada, já que o sistema não tem a estabilidade necessária. Para cumprir com este objetivo seis estudos de caso foram conduzidos e os resultados encontrados, suportados pela teoria, sugerem o aparecimento de um modelo híbrido eficaz para planejamento no ambiente estudado assim como o aparecimento de um sistema DSS (Decision Support System). Outra contribuição desta pesquisa foi identificar, em um dos casos, uma empresa que conseguiu atacar de maneira eficaz o fenômeno em sua causa raiz neutralizando assim seus efeitos. / The highly competitive environment of modern times has put pressure on the decision-making process in the corporate world. The trade-offs of competitive priorities such as cost, quality, service and flexibility are no longer enough. These trade-offs, albeit important in the short term, must be matched so that companies that have the best balance between them should have superior results. One of the tradeoffs widely discussed is the balance between service level and inventory. The perception is that excellence is not likely to be achieved in service without having a significant level of inventory. From this scenario comes the paradox of using MRP systems (Material Requirement Planning) versus JIT systems (Just in Time), or rather \"pushed\" systems versus \"pulled\" systems since the option for one or the other system has a close connection with inventory management. On the one hand, MRP systems are widely used in industry through ERP software; on the other hand, JIT systems have obtained better results. While many companies consider adopting one or another system, some of them adopt a hybrid process with the goal of taking the best of each system and generate superior performance. The purpose of this research is to investigate how companies inserted in markets characterized by sales peak at the end of the month (hockey-stick phenomenon), and low accuracy in demand forecasts, are applying their production planning strategies and their ERP. Low forecast accuracy causes a problem in applying pushed strategies as it requires a high safety stock associated. Conversely, the sales peak hinders the adoption of a purely pull strategy since the system does not have the necessary stability. To meet this goal, six case studies were conducted and the results found and supported by the theory suggest the emergence of an effective hybrid model for planning in the environment studied as well as the appearance of a DSS (Decision Support System). Another contribution of this research was to identify in one of the cases a company that managed to effectively tackle the phenomenon in the root cause, neutralizing its effects.

Les molécules organométalliques présentant d’intéressantes propriétés, notamment en optique non linéaire (ONL), en luminescence et en photovoltaïque, trouvent leur utilité dans la préparation de nouveaux matériaux pour des applications dans les domaines de l’optoélectronique, de la photonique et des cellules solaires à colorant photosensible (DSSC). Ce manuscrit de thèse présente la synthèse et les résultats des propriétés ONL du second ordre de nouveaux complexes dissymétriques push-pull de motif D–π–M–π–A et basés sur les diacétylures de platine (II), les diacétylures de ruthénium (II) et les dérivés du ferrocène. Ces complexes sont constitués de ligands du méthylènepyrane en tant que groupes électrodonneurs pro-aromatiques (D) et de ligands formaldéhyde, indane-1,3-dione, pyrazine, pyrimidine ou iodure de pyrimidinium en tant que groupes électroattracteurs (A), ces deux groupes étant séparés par le centre métallique et différents espaceurs π-conjugués. La réponse en optique non linéaire (ONL) du second ordre des complexes a été mesurée à l’aide de la méthode EFISH (Electric-Field-Induced Second Harmonic) et a été comparée à celle de leurs analogues tout organiques. Tous les complexes ont donné des valeurs µβ de la réponse ONL, fortement augmentées par la méthylation de la pyrimidine. En utilisant les mêmes types de groupes électrodonneurs et électroattracteurs, les plus fortes réponses ONL ont été obtenues avec les complexes de ruthénium. Pour l’un d’entre-eux, une valeur µβ0 particulièrement élevée de 6000.10-48 esu a pu être mesurée. / Organometallic molecular systems exhibiting interesting properties, such as non-linear optical (NLO) responses, luminescence and energy photoconversion, are of great interest in the preparation of novel materials with potential applications in opto-electronics, photonics and Dye-Sensitized Solar Cells (DSSC). This manuscript highlights the synthesis, characterization and the second-order NLO properties of new asymmetrical D–π–M–π–A push–pull dialkynyl ruthenium- and platinum-based as well as dialkenyl ferrocene-based complexes. All complexes incorporate pyranylidene ligands as pro-aromatic donor groups (D) and formaldehyde, indane-1,3-dione pyrazine, pyrimidine or pyrimidinium iodide as electron-withdrawing groups (A) separated by the metal fragment and various π-linkers. The second order nonlinear optical (NLO) properties of all complexes were measured by the electric-field-induced second harmonic generation (EFISH) technique and compared to those of their purely organic analogs. All complexes exhibited µβ values, which dramatically increased upon methylation of the pyrimidine group. With the same donor–acceptor group combination, the strongest NLO response was obtained with the ruthenium complexes, which exhibited a remarkably high µβ0 value of 6000.10-48 esu.

Os comprimidos osmóticos do tipo bicamada ou \"push pull\" são sistemas reservatórios constituídos de um núcleo bicamada, circundado por uma membrana semipermeável e com um orifício de liberação perfurado a laser que permitem a liberação do fármaco através da cinética de ordem zero. Este sistema possui a vantagem de apresentar uma liberação controlada e não influenciada pelos fatores fisiológicos do trato gastrointestinal, permitindo aplicações terapêuticas para novos fármacos e inclusive para fármacos já existentes. O presente projeto contemplou as etapas de desenvolvimento, caracterização e avaliação de um sistema osmótico do tipo bicamada ou \"push pull\", para veiculação do atenolol, um beta bloquador de grande importância na terapia antihipertensiva. Após a padronização e validação da metodologia analítica, estudos de compatibilidade entre o fármaco e os excipientes através da análise calorimétrica e espectroscopia no infravermelho (pré-formulação), a produção, a caracterização da membrana de revestimento e, por fim, a avaliação do desempenho dos núcleos osmóticos foram realizados. Assim, três lotes, com 4kg cada, foram produzidos para determinação do peso médio e do ferramental adequados, além da proporção entre os excipientes da formulação. O processo de compressão deu origem aos núcleos osmóticos do tipo bicamada que foram submetidos à avaliação físico-química como determinação do peso médio, da dureza, da friabilidade e da espessura. Além disso, padronizou-se o processo de revestimento dos núcleos com membrana semipermeável e avaliou-se o perfil de captação de água dos núcleos resultantes (\"Swelling\"). A membrana de revestimento foi submetida à microscopia eletrônica de varredura (MEV), análise por adsorção de nitrogênio e porosimetria de mercúrio para verificação da distribuição e tamanho médio dos poros. Para a obtenção do orifício de liberação padronizou-se a quantidade de radiação a laser suficiente para perfuração da membrana semipermeável que envolve os núcleos. Após a perfuração a laser, os núcleos foram submetidos então ao estudo de liberação in vitro para avaliação da influência do diâmetro de orifícios, do número de orifícios, da espessura da membrana semipermeável, da hidrodinâmica do meio de dissolução e da influência térmica na velocidade de liberação do fármaco. A cinética do tipo ordem zero e o controle da liberação do fármaco ao longo do tempo foram alcançados com sucesso a partir dos núcleos osmóticos produzidos no lote 03. / The push pull osmotic release tablets are bilayer core reservoir systems surrounded by semi permeable membrane and with one delivery hole where the drug is released through, following zero order release kinetics. This system has many advantages and two of them are the controlled drug release and independence of physiologically factors allowing many therapeutic applications to new one and known one drugs. This exclusive work proposed the development, characterization and evaluation of atenolol push pull osmotic system that is very important to antihypertensive treatment. After analytical standardization and validation activities, the pre-formulation studies using calorimetric and infra red spectroscopy techniques, manufacturing, semi permeable membrane characterization and finally osmotic tablets performance evaluation were performed. Batches about 4 kg each one were manufactured and tablets average weight, by-layer proportionality and suitable punches were chosen. Thus the osmotic tablets obtained by bi-layer press were physical and chemical evaluated (average weight, hardness, friability, and thickness). After that the tablets were submitted to a coating process with semi permeable membrane and the uptake water profile (Swelling) was observed to characterize the membrane permeability. The semi permeable membrane was submitted also to scanning electron microscopy (SEM), nitrogen adsorption and mercury porosimetry techniques in order to characterize the porous average diameter and distribution. To produce the delivery hole in the drug layer semi permeable membrane the sufficient laser radiation amount was studied and determined. So the perforated osmotic tablets were submitted to in vitro drug release studies to evaluate the influence of hole diameter, hole number, coating thickness, medium hydrodynamic and temperature stress responsible for drug release modifications. Finally the controlled delivery and the zero order drug release kinetics were achieved successfully from osmotic tablets developed and produced in the third bath. This third bath was the result of the factors comprehension and the optimization of the early ones.

O ambiente competitivo atual tem colocado pressão no processo de tomada de decisão no mundo corporativo. Os trade-offs das prioridades competitivas discutidos na elaboração da estratégia como custo, qualidade, serviço e flexibilidade já não são suficientes. Estes trade-offs, embora importantes no curto prazo, devem ser compatibilizados de modo que as empresas que tenham o melhor balanço entre eles devam ter resultado superior. Um dos trade-offs bastante discutido é o equilíbrio entre serviço e estoque. A percepção é que seja improvável alcançar excelência no serviço sem ter um considerável nível de estoque. Deste cenário nasce então o paradoxo do uso de sistemas MRP (Material Requirement Planning) versus sistemas JIT (Just in Time), ou melhor, sistemas empurrados versus puxados, já que a escolha por um ou outro sistema tem ligação íntima com a gestão de estoque. Se por um lado os sistemas MRP são largamente utilizados, via softwares ERP, por outro sistemas JIT têm trazido importantes melhorias nos resultados. Embora muitas empresas considerem a adoção exclusiva de um ou outro sistema, algumas delas têm adotado um processo híbrido com o objetivo de tirar o melhor de cada sistema e gerar assim desempenho superior. O objetivo deste trabalho é investigar como as empresas inseridas em mercados caracterizados pela concentração de demanda no final do mês (fenômeno conhecido como hockey-stick), e baixo acerto nas previsões de demanda, estão aplicando suas estratégias de planejamento de produção e seus ERP. Se por um lado a baixa acurácia nas previsões causa um problema na aplicação de estratégias empurradas de planejamento, pois requer um alto estoque de segurança associado, por outro a concentração de embarque dificulta a adoção de uma estratégia puramente puxada, já que o sistema não tem a estabilidade necessária. Para cumprir com este objetivo seis estudos de caso foram conduzidos e os resultados encontrados, suportados pela teoria, sugerem o aparecimento de um modelo híbrido eficaz para planejamento no ambiente estudado assim como o aparecimento de um sistema DSS (Decision Support System). Outra contribuição desta pesquisa foi identificar, em um dos casos, uma empresa que conseguiu atacar de maneira eficaz o fenômeno em sua causa raiz neutralizando assim seus efeitos. / The highly competitive environment of modern times has put pressure on the decision-making process in the corporate world. The trade-offs of competitive priorities such as cost, quality, service and flexibility are no longer enough. These trade-offs, albeit important in the short term, must be matched so that companies that have the best balance between them should have superior results. One of the tradeoffs widely discussed is the balance between service level and inventory. The perception is that excellence is not likely to be achieved in service without having a significant level of inventory. From this scenario comes the paradox of using MRP systems (Material Requirement Planning) versus JIT systems (Just in Time), or rather \"pushed\" systems versus \"pulled\" systems since the option for one or the other system has a close connection with inventory management. On the one hand, MRP systems are widely used in industry through ERP software; on the other hand, JIT systems have obtained better results. While many companies consider adopting one or another system, some of them adopt a hybrid process with the goal of taking the best of each system and generate superior performance. The purpose of this research is to investigate how companies inserted in markets characterized by sales peak at the end of the month (hockey-stick phenomenon), and low accuracy in demand forecasts, are applying their production planning strategies and their ERP. Low forecast accuracy causes a problem in applying pushed strategies as it requires a high safety stock associated. Conversely, the sales peak hinders the adoption of a purely pull strategy since the system does not have the necessary stability. To meet this goal, six case studies were conducted and the results found and supported by the theory suggest the emergence of an effective hybrid model for planning in the environment studied as well as the appearance of a DSS (Decision Support System). Another contribution of this research was to identify in one of the cases a company that managed to effectively tackle the phenomenon in the root cause, neutralizing its effects.

Os comprimidos osmóticos do tipo bicamada ou \"push pull\" são sistemas reservatórios constituídos de um núcleo bicamada, circundado por uma membrana semipermeável e com um orifício de liberação perfurado a laser que permitem a liberação do fármaco através da cinética de ordem zero. Este sistema possui a vantagem de apresentar uma liberação controlada e não influenciada pelos fatores fisiológicos do trato gastrointestinal, permitindo aplicações terapêuticas para novos fármacos e inclusive para fármacos já existentes. O presente projeto contemplou as etapas de desenvolvimento, caracterização e avaliação de um sistema osmótico do tipo bicamada ou \"push pull\", para veiculação do atenolol, um beta bloquador de grande importância na terapia antihipertensiva. Após a padronização e validação da metodologia analítica, estudos de compatibilidade entre o fármaco e os excipientes através da análise calorimétrica e espectroscopia no infravermelho (pré-formulação), a produção, a caracterização da membrana de revestimento e, por fim, a avaliação do desempenho dos núcleos osmóticos foram realizados. Assim, três lotes, com 4kg cada, foram produzidos para determinação do peso médio e do ferramental adequados, além da proporção entre os excipientes da formulação. O processo de compressão deu origem aos núcleos osmóticos do tipo bicamada que foram submetidos à avaliação físico-química como determinação do peso médio, da dureza, da friabilidade e da espessura. Além disso, padronizou-se o processo de revestimento dos núcleos com membrana semipermeável e avaliou-se o perfil de captação de água dos núcleos resultantes (\"Swelling\"). A membrana de revestimento foi submetida à microscopia eletrônica de varredura (MEV), análise por adsorção de nitrogênio e porosimetria de mercúrio para verificação da distribuição e tamanho médio dos poros. Para a obtenção do orifício de liberação padronizou-se a quantidade de radiação a laser suficiente para perfuração da membrana semipermeável que envolve os núcleos. Após a perfuração a laser, os núcleos foram submetidos então ao estudo de liberação in vitro para avaliação da influência do diâmetro de orifícios, do número de orifícios, da espessura da membrana semipermeável, da hidrodinâmica do meio de dissolução e da influência térmica na velocidade de liberação do fármaco. A cinética do tipo ordem zero e o controle da liberação do fármaco ao longo do tempo foram alcançados com sucesso a partir dos núcleos osmóticos produzidos no lote 03. / The push pull osmotic release tablets are bilayer core reservoir systems surrounded by semi permeable membrane and with one delivery hole where the drug is released through, following zero order release kinetics. This system has many advantages and two of them are the controlled drug release and independence of physiologically factors allowing many therapeutic applications to new one and known one drugs. This exclusive work proposed the development, characterization and evaluation of atenolol push pull osmotic system that is very important to antihypertensive treatment. After analytical standardization and validation activities, the pre-formulation studies using calorimetric and infra red spectroscopy techniques, manufacturing, semi permeable membrane characterization and finally osmotic tablets performance evaluation were performed. Batches about 4 kg each one were manufactured and tablets average weight, by-layer proportionality and suitable punches were chosen. Thus the osmotic tablets obtained by bi-layer press were physical and chemical evaluated (average weight, hardness, friability, and thickness). After that the tablets were submitted to a coating process with semi permeable membrane and the uptake water profile (Swelling) was observed to characterize the membrane permeability. The semi permeable membrane was submitted also to scanning electron microscopy (SEM), nitrogen adsorption and mercury porosimetry techniques in order to characterize the porous average diameter and distribution. To produce the delivery hole in the drug layer semi permeable membrane the sufficient laser radiation amount was studied and determined. So the perforated osmotic tablets were submitted to in vitro drug release studies to evaluate the influence of hole diameter, hole number, coating thickness, medium hydrodynamic and temperature stress responsible for drug release modifications. Finally the controlled delivery and the zero order drug release kinetics were achieved successfully from osmotic tablets developed and produced in the third bath. This third bath was the result of the factors comprehension and the optimization of the early ones.

Le pou rouge Dermanyssus gallinae est un acarien d’importance sanitaire et économique majeure en élevage de poules pondeuses partout dans le monde mais paradoxalement le fonctionnement de son écosystème a été relativement peu étudié. Hématophage strict, D. gallinae n’est pas un parasite typique, il entretient une relation lâche mais obligatoire avec son hôte. Confiné dans l’environnement proche de son hôte (nids, fientes sèches, litière, fumier, . . .) D. gallinae est fortement soumis aux interactions avec les autres organismes qui peuplent ces microhabitats. Ce travail a pour objectif d’apporter des éléments pertinents de caractérisation de cet écosystème singulier mal connu pour, au delà de la production de connaissance, alimenter une réflexion sur le développement de stratégies de gestion intégrée innovantes afin de s’affranchir de la stricte lutte chimique qui reste à l’heure actuelle le moyen de luttele plus largement utilisé. L’étude des interactions chimiques entre le pou rouge et son hôte a permis de mieux identifier les sources de stimulus et mieux comprendre les réponses de D. gallinae aux odeurs de poule ainsi que de déterminer dans quelle mesure il était possible d’interférer entre l’hôte et son microprédateur au moment de l’étape de repérage. La caractérisation de la structure des communautés d’arthropodes partageant les mêmes microhabitats que le pou rouge a montré que D. gallinae côtoyait plusieurs espèces d’acariens et insectes prédateurs d’arthropodes qui sont potentiellement ses ennemis naturels. Il a également été mis en évidence que le bâtiment d’élevage constituait une unité propre en termes de composition et de structure des communautés d’arthropodes. Les différences significatives de fréquence et d’occurrencedes différentes espèces prédatrices entre bâtiments, ainsi que leur capacitéde propagation depuis l’environnement extérieur constituent des indicateurs prometteurs pour le développement de la lutte biologique par conservation contre le pou rouge. Des questions transversales quant aux effets croisés, synergiques ou antagonistes, entre la manipulation des odeurs de l’hôte et la mise à contribution des processus écologiques impliquant les arthropodes non hématophages sont posées en vue d’une démarche intégrant ces outils ainsi que les autres moyens de contrôle disponibles dans un contexte de protection biologique intégrée du pou rouge. / The Poultry Red Mite (PRM) Dermanyssus gallinae is a mite of major sanitary andeconomic importance for the egg production industry worldwide but paradoxicallythe functioning of its ecosystem has been little studied. The objective of this work was to provide relevant elements for the characterization of this singular ecosystem that is poorly known, in order to, beyond the production of knowledge, contribute to the development of innovative strategies of integrated management. This is expected to allow going further than the strict chemical control which is still to date the most widely used means of control. The study of the chemical interactions between the PRM and its host allowed to better identify sources of stimulus and to better understand D. gallinae’s responses to chicken odors as well as to determine to what extent it was possible to interfere between the host and its micropredator during the first phase of the host location. The characterization of the structure of arthropod communities sharing the same microhabitats as does PRM showed that D. gallinae was associated with several species of mites and predatory insects of arthropods which could potentially be its natural enemies. It was also demonstrated that the livestock building was a specific unit in terms of the composition and structure ofthe arthropod communities. Significant differences in the frequency and occurrence of predatory species between buildings and their propagation capacity from the external environment are promising indicators for the development of conservation biological control (CBC) against PRM. A reflection on the possible synergistic and antagonistic cross-effects between the manipulation of host odors and the stimulation of ecological processes involving non-haematophagous arthropods is carried out. This is expected to participate in the development of an approach integrating these tools as well as other available means of control in a context of integrated biological protection of PRM.

Au cours des dernières années, le développement des cellules organiques à réseaux interpénétrés a permis d’améliorer les rendements de conversion photovoltaïque (PV). Ces dispositifs incorporent une couche active constituée d’un mélange d’un matériau donneur d’électron (D) et d’un matériau accepteur d’électron (A). La réalisation de ces cellules requiert une optimisation minutieuse de ce mélange et de la morphologie de cette couche photo-active qui en résulte. Cette dernière peut cependant évoluer spontanément vers une ségrégation de phase, généralement délétère pour les performances PV. Une solution possible, et relativement peu étudiée, consiste à lier chimiquement le donneur D et l’accepteur A par un espaceur non-conjugué. Les travaux décrits dans ce manuscrit portent sur la synthèse et la caractérisation d’assemblages moléculaires de type D-σ-A ainsi que leur utilisation comme matériau dit « unique » pour la fabrication de cellules solaires organiques mono composant. Une première famille de dyades et triades à base d’un bloc donneur de type quaterthiophène a été étudiée. Cette partie décrit la méthodologie générale d’assemblage des blocs D et A via une réaction de cycloaddition de type Huisgen. Au cours des chapitres suivant, plusieurs dyades basées sur un bloc donneur « push-pull » ont été synthétisées puis caractérisées. Les performances PV de ces composés ont été évaluées au sein de cellules solaires mono-composant et les meilleurs rendements de conversion, atteignant 1.4 %, rivalisent avec l’état de l’art. / Over the last few years, the development of bulk heterojunction organic solar cells (BHJ OSCs) led to significant increase in photovoltaic (PV) efficiency. Such devices are based on interpenetrated networks of an electron-donor material (D) and an electron-acceptor material (A) constituting the active layer. Nevertheless a careful optimization of the morphology is required to reach high power conversion efficiency. Furthermore, this optimized morphology can evolve towards spontaneous phase segregation which can be detrimental for the PV performances. To circumvent these limitations, a relatively unexplored approach relies on the use of a material where the donor and the acceptor moieties are covalently linked to each other through a nonconjugated π-connector. In this context, the work reported herein describes the synthesis and characterization of various molecular D-σ-A assemblies, as well as their preliminary evaluation as “unique” material for the realisation of single component organic solar cells (SC-OSCs). A first family of dyads and triads, based on quaterthiophene moieties as donor block, was studied. A general methodology to assemble the two D and A blocks via a Huisgen-type click-chemistry is described. Then, in the next chapters, several dyads based on a “push-pull” donor block have been synthesized and characterized. The PV performances of these compounds have been evaluated in SC-OSCs leading to power conversion efficiency up to 1.4 %, a value close to the state of the art.

Au cours des dernières décennies, les chromophores organiques “push-pull” ont vu leur intérêt grandir en raison de leurs applications potentielles dans les domaines des transistors à effet de champ, de l'optique non linéaire, des OLEDs, et du photovoltaïque. Dans le cadre de la conception de cellules photovoltaïques, ces structures moléculaires correctement organisées sur une surface devraient permettre d’améliorer l’interface donneur/accepteur, l’absorption optique, et d’augmenter le volume de la couche active. Nous avons développé une synthèse en plusieurs étapes de nouvelles molécules “push-pull” comportant une tête réactive thiol autorisant la formation de monocouches moléculaires auto-assemblées (SAM) sur surfaces d’or ou d’ITO. En variant les groupements donneur, accepteur, et l’espaceur il a été possible de moduler les propriétés optiques et électroniques.Les produits obtenus possèdent une forte absorption de lumière et peuvent donc être efficaces pour le photovoltaïque. Les monocouches moléculaires finales des chromophores avec ou sans nanoparticules d’or ont été étudiées principalement par angles de contact, techniques de spectroscopie IR, UV-Vis, XPS, et par microscopie à sonde locale (STM, AFM). Les matériaux ainsi obtenus à base de SAMs de chromophores “push-pull” et de nanoparticules de métaux nobles ont ensuite caractérisés électriquement et optiquement pour évaluer leur utilisation potentielle pour la conversion de l’énergie photovoltaïque. / During the past decades, the synthesis of organic donor-acceptor (D/A) “push-pull” chromophores has been of considerable interest because of their potential use in nonlinear optics, LEDs, field effect transistors, and photovoltaics (PV). As a part of the design of the PV cells, these molecular structures correctly arranged on a surface should improve the donor/acceptor interface, the optical absorption, and increase the volume of the active layer. We have developed a multi-step synthesis of new “push-pull” molecules bearing a thiol reactive group enabling to form self-assembled monolayers (SAM) on gold or ITO surfaces. Combining various donor, acceptor, and spacer moieties we could tune the “push-pull” optical and electronic properties. The obtained “push-pull” products exhibit a high light absorption and can thus be effective in PV applications. Final SAMs with and without nanoparticles were studied mainly by contact angles, UV-vis, IR and XPS spectroscopy, ellipsometry and near-field microscopy (STM and AFM). As-obtained organic layers were then electrically and optically characterized to assess their potential use in the field of PV energy conversion.