Ce travail porte sur la synthèse, la caractérisation et l’évaluation en catalyse de réduction des protons en dihydrogène, de nouveaux complexes de Ni(II), Co(III), Cu(II) et Pd(II) basés sur des ligands de type thiosemicarbazone. La nature de l’espèce catalytique active a été étudiée par voltampérométrie cyclique et des propositions de mécanisme ont été formulés sur la base de calcul quantique de type DFT.Le premier chapitre introduit le contexte scientifique. Le second chapitre concerne la synthèse et la caractérisation des ligands de type N2S2 et des complexes mononucléaires associés de Ni, Cu et Pd. Le troisième chapitre présente la synthèse et la caractérisation de complexes binucléaires de Co et trinucléaire de Ni.Les études électrochimiques de ces complexes dans le DMF en présence d’une source de protons, nous a permis d’évaluer leur efficacité catalytique. Nos résultats montrent que les complexes du Cu et du Pd présentent une vague irréversible spécifique pour la réduction des protons, mais une décomposition est observée durant l’électrolyse. Par contre, les complexes de Ni et de Co ont montré une stabilité électrochimique ainsi que de bonnes performances catalytiques. En particulier, le nouveau complexe mononucléaire de Ni présente des propriétés catalytiques remarquables qui le classent parmi les meilleurs catalyseurs de la réduction des protons décrits dans la littérature. L’ensemble de ce travail fourni une description complète du comportement électrochimique des ligands de type N2S2 complexés à des métaux de transition. Il permet d’envisager des développements futurs dans l’amélioration des propriétés catalytiques de ces complexes. / This work focuses on the synthesis, the characterization and the catalytic evaluation in the reduction of protons into dihydrogen, of new complexes of Ni(II), Co(III), Cu(II) and Pd(II) based ligands Type thiosemicarbazone. The catalytically active species during the process of the proton reduction was studied by cyclic voltammetry and mechanisms were formulated on the basis quantum chemical calculation.The first chapter introduces the scientific context, the goals and the main objectives of this work. The second chapter concerns the synthesis and the characterization of the N2S2 ligands and their associated mononuclear complexes, Ni, Cu and Pd. The third chapter presents the synthesis and the characterization of binuclear Co and trinuclear Ni based on N2S2 ligand.Electrochemical studies of these complexes in DMF in the presence of a proton source (trifluoroacetic acid), allowed us to evaluate their catalytic efficiency. Our results show that Cu and Pd complexes have a specific irreversible wave for the reduction of protons, but decomposition is observed during electrolysis, which makes these uninteresting complexes for the reduction of protons.On the contrary, Ni and Co complexes showed an electrochemical stability and good catalytic performances. In particular, the new mononuclear Ni complex exhibits remarkable catalytic properties that rank it among the best catalysts for the reduction of protons reported in the literature. All this work provided a complete description of the electrochemical behavior of N2S2 thiosemicarbazone ligands complexed to transition metals. It allows considering future developments in improving the catalytic properties of these complexes.

Enzymes are high-weight molecules which catalyze most of the metabolic processes in living organisms. Very often, these proteins contain one or more 1st row transition metal ions in their active center (Fe, Cu, Co, Mn, Zn, etc.), and are known as metalloenzymes or metalloproteins. Among these, metalloenzymes that activate molecular oxygen and use it as terminal oxidant stand out because of the wide range of catalyzed reactions and their exquisite selectivity. In this PhD dissertation we develop low-weight synthetic bioinspired complexes that can mimic structural and/or functional features of the active center of oxigenases. In the first part, we describe the use of unsymmetric dinuclear Cu complexes which are capable of performing the oxidation of phenols and phenolates in a analogous manner of the tyrosinase protein. In the second part, we describe the use of mononuclear manganese complexes in the oxidation of alcanes and alquenes. / Els enzims són molècules d’elevat pes molecular que catalitzen la majoria de processos metabòlics en els éssers vius. Sovint aquestes proteïnes contenen un o diversos ions metàl•lics de la 1a sèrie de transició en el seu centre actiu (Fe, Cu, Co, Mn, Zn, etc.), essent anomenats metal•loenzims o metal•loproteïnes. D’aquests, els metal•loenzims que activen la molècula d’oxigen i l’utilitzen com a oxidant ressalten per la varietat de reaccions catalitzades i la seva exquisida selectivitat. En aquesta tesi doctoral, desenvolupem complexos de baix pes molecular que puguin mimetitzar estructural i/o funcionalment els centres actius de les oxigenases. En una primera part, es descriu la utilització de complexos assimètrics dinuclears de Cu capaços de dur a terme l'oxidació de fenols i fenolats de manera similar a la proteïna tirosinasa. En una segona part, es descriu l'ús de complexos mononuclears de manganès per a l'oxidació d'alcans i alquens.

No description available.

Bioinspirierte Polymere, die die Multidomänenstruktur des Muskelproteins Titin imitieren, wurden auf Grundlage von zuvor synthetisierten, zyklischen Präpolymeren, die Wasserstoffbrückenbindungen-tragende Monomere enthalten, hergestellt und hinsichtlich ihrer mechanischen Eigenschaften untersucht.  Zunächst wurde die Ringexpansionspolymerisation (REP) zur Erzeugung zyklischer Makromoleküle, die auf einer von Nishikubo et al. entwickelten, lebenden Gruppentransferpolymerisation von Thiiranmonomeren mit Acylgruppen-tragenden Initiatoren basiert, eingehend untersucht. Im Speziellen wurde ein System, bestehend aus dem zyklischen Initiator 2,4-Thiazolidindion (TZD) und Derivaten desselben, dem Katalysator Tetrabutylammoniumchlorid, verschiedenartig substituierten Thiiranmonomeren 2-(Phenoxymethyl)thiiran (PMT), 2-Methylthiiran (MT), 2-(tert-Butoxymethyl)thiiran (TBMT), 2-((o-Methylphenoxy)methyl)thiiran (MPMT) und dem Lösungsmittel N-Methylpyrrolidin-2-on verwendet. Bei der Insertion der Monomere MT, TBMT und MPMT in TZD, die unter guter Kontrolle des Polymerisationsgrads und der Dispersität stattfand, wurde eine Verschmelzung der Ringe zu größeren Ringstrukturen mit einem Verschmelzungsgrad von bis zu zwei, bei Verwendung von PMT sogar von bis zu vier beobachtet. Der Grad dieser Verschmelzung nahm im Fall von PMT mit zunehmender Monomerkonzentration, zunehmendem molaren Monomer-zu-Initiator-Verhältnis und zunehmender Reaktionstemperatur ab, während er bei den anderen Monomeren keine Konzentrations- und Temperaturabhängigkeit zeigte. Durch Anpassung der Molmassenverteilungen mittels einer Summe von Gauß-Funktionen im Fall der PMT-Polymere konnte die zeitliche Änderung der molaren Anteile der verschiedenen Ringspezies verfolgt werden. So wurden für Polymerkonzentrationen von 14 bis 52 Gew-% Geschwindigkeitskoeffizienten der Verschmelzung, die sich über Größenordnungen von 10^(−2) bis 10^(−6) L/mol/s erstrecken, ermittelt. Bei Verwendung von in 3-Position substituierten TZD-Derivaten wurde eine Zunahme der Anzahl verschmolzener Makrozyklen von bis zu sieben festgestellt. Die Bildung zyklischer Strukturen wurde mittels Massenspektrometrie und rasterkraftmikroskopischer (AFM) Aufnahmen gezeigt.  Neben den Homopolymerisationen wurden zyklische (AB)n-Multiblockcopolymere aus MT und PMT mit bis zu acht aus der Ringverschmelzung resultierenden Blöcken synthetisiert. Sie zeigten im Zugversuch, aufgrund der verschiedenen Topologien, im Vergleich zu linearen Diblockcopolymeren ähnlicher Zusammensetzung, deutliche Unterschiede in der maximalen Zugdehnung und der Zähigkeit.  Weiterhin wurden die eingangs erwähnten bioinspirierten Polymere durch Kombination von zyklischen und linearen Segmenten hergestellt und auf ihre mechanischen Eigenschaften untersucht. Dazu wurden zyklische (ABC)n-Multiblockcopolymere, die zusätzlich einen kurzen Block des Monomers Ethyl-2-(4-(thiiran-2-ylmethoxy)benzamido)acetat (ETBAA) enthielten, der zur Ausbildung selbstkomplementärer Wasserstoffbrückenbindungen in der Lage ist, synthetisiert. Diese Präpolymere wurden mittels 1,3-dipolarer Cycloaddition in einer Polyadditionsreaktion mit einem niedermolekularen, bifunktionellen Verknüpfungsagens oder mit monofunktionellem Poly-n-butylacrylat (PBA) bzw. Polymethylacrylat (PMA), welche mittels RAFT-Polymerisation hergestellt wurden, verknüpft. So konnte im ersten Fall eine Poly-Ringpolymer-Topologie mit bis zu 19 nachgewiesenen Wiederholeinheiten und im zweiten Fall ein Polymer mit Kette–Ring–Kette-Topologie erhalten werden.  Untersuchungen der Proben im Zugversuch zeigten beim Kette–Ring–Kette-Polymer bis auf eine höhere Elastizität keine verbesserten Materialeigenschaften im Vergleich zum linearen PMA-Präpolymer. Die Poly-Ringpolymere hingegen zeigten im Gegensatz zu den Ringpolymeren ein einzigartiges Spannungs-Dehnungsverhalten, bessere Elastizitätseigenschaften und eine Erhöhung der anwendbaren Spannung bei gleicher Dehnung. Dies wurde durch den Einfluss inter- und intramolekular ausgebildeter physikalischer Bindungen durch die enthaltenen selbstkomplementären Wasserstoffbrückenbindungsmotive hervorgerufen. Eines der untersuchten Poly-Ringpolymere zeigte aufgrund der Ausbildung eines reversiblen physikalischen Netzwerkes sogar ein Formgedächtnis und die Fähigkeit zu einer partiellen Selbstheilung.

Apprenant de la nature, les architectures spécifiques de certains organismes vivants sont devenues l'une des idées dominantes dans le développement de nouvelles générations de matériaux synthétiques. Dans cette optique, la structure lamellaire de la nacre peut servir de modèle pour la fabrication de nouveaux matériaux composites à matrices métalliques. Un nouveau procédé de métallurgie des poudres, appelée métallurgie des poudres « plaquettes » (FPM), a ainsi été développée pour fabriquer des matériaux composites à matrice métallique à structure lamellaire.L’objectif de ce travail de thèse est l'utilisation du procédé FPM (en utilisant le broyage mécanique (BM) et le frittage SPS), pour la fabrication de matériaux architecturés lamellaires et bioinspirés de structure nacre. Nous avons montré la possibilité de fabriquer, à partir de poudre plaquettes, des matériaux lamellaires anisotropes monolithiques à base de titane et d’alliages de titane ainsi que des matériaux composites Ti/C. Nous avons également montré les avantages de l'architecture multicouches sur l'amélioration des propriétés mécaniques (dureté) du Ti et de TA6V avec une anisotropie de la dureté entre les sections transversale et longitudinale. L’augmentation de la dureté de ces matériaux lamellaires, par rapport aux matériaux non-lamellaire, est liée principalement à l'épaisseur des "plaquettes" qui est contrôlée par le temps de BM, ainsi que par l’effet de la microstructure affinée et de l’écrouissage du matériau lamellaire.Nous avons également montré la possibilité de fabriquer des matériaux composites lamellaires in-situ Ti/TiC par BM (en présence d'acide stéarique) et frittage SPS, avec la possibilité de contrôler la teneur en TiC en jouant sur les conditions de BM (temps BM et taux d’acide stéarique). Ce matériau composite permet une amélioration de la dureté et du module de Young attribuée à la phase de TiC formée. / Learning from nature, biological design has become one of the prevailing ideas in developing new generations of synthetic materials. In the strengthening and toughening exploration of composite materials, nacre lamellar structure may serves as a model system of tremendous interest. A novel powder metallurgy (PM) strategy, called flake PM, was developed to fabricate bulk metal matrix composite materials with laminated structure.The aims of this thesis is the use of flakes PM (using ball milling and SPS sintering), for the fabrication of biomimetic titanium and titanium alloys nacre’s laminated structures and of titanium/carbon composite materials. This process showed the possibility of the fabrication of laminar material with anisotropic microstructure. We proved the advantages of the layer’s architecture on the improvement of Ti and TA6V mechanical properties (hardness) with hardness anisotropy between the cross section and the longitudinal one. The hardness of this material is related to the thickness of the "flakes" which is controlled by the time of BM. This strengthening was also attributed to the flake thickness, the refined microstructure and the hardening of the lamellar material.We showed also the possibility of fabrication of in-situ Ti/TiC laminated composite materials using BM (in the presence of stearic acid) and SPS sintering, with the possibility of the control of TiC content by controlling the BM conditions (BM time and stearic acid amount). This composite material exhibit improvement of the hardness and Young’s modulus, attributed to the TiC phase formed.

Orientadores: Fernando Jose Von Zuben, Leandro Nunes de Castro Silva / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Eletrica e Computação / Made available in DSpace on 2018-08-06T14:08:06Z (GMT). No. of bitstreams: 1 Vargas_PatriciaAmancio_D.pdf: 4626705 bytes, checksum: b203a58e3f5f1c613db0787b3e396196 (MD5) Previous issue date: 2005 / Resumo: Este trabalho propõe uma classificação circunstancial para sistemas complexos, incluindo uma estrutura unificada de descrição a ser empregada na análise e síntese de sistemas computacionais bio-inspirados. Como um ramo dos sistemas complexos organizados, os sistemas computacionais bio-inspirados admitem uma sub-divisão em sistemas de inteligência computacional e sistemas homeostáticos artificiais. Com base neste formalismo, duas abordagens híbridas são concebidas e aplicadas em problemas de navegação autônoma de robôs. A primeira abordagem envolve sistemas classificadores com aprendizado e sistemas imunológicos artificiais, visando explorar conjuntamente conceitos intrínsecos a sistemas complexos, como auto-organização, evolução e cognição dinâmica. Fundamentada nas interações neuro-imuno-endócrinas do corpo humano, a segunda abordagem propõe um novo modelo de sistema homeostático artificial, explorando mudanças de contexto e efeitos do meio sobre o comportamento autônomo de um robô móvel. Embora preliminares, os resultados obtidos envolvem simulação computacional em ambientes virtuais e alguns experimentos com robôs reais, permitindo extrair conclusões relevantes acerca do potencial das abordagens propostas e abrindo perspectivas para a síntese de sistemas complexos adaptativos de interesse prático / Abstract: This work proposes a circumstantial classification for complex systems, including a unified description structure to be employed in the analysis and synthesis of biologically inspired computing metaphors. Considered as a branch of organized complex systems, these bio-inspired computing frameworks may be subdivided into computation intelligence systems and artificial homeostatic systems. Developed under this formalism, two novel hybrid systems are conceived and applied to robot autonomous navigation problems. The first approach involves learning classifier systems and artificial immune systems, in an attempt to investigate intrinsic concepts of complex systems as self-organization, evolution, and dynamic cognition. Drawn on the principles of the human nervous, immune and endocrine systems, the second approach envisages a new model of an artificial homeostatic system to explore context changes and environmental effects on the behaviour of an autonomous robotic agent. Though preliminary, the obtained results encompass computer simulation on virtual environments in addition to a number of real robot¿s experiments. Relevant conclusions can be invoked, mainly related to the potentiality of the proposed frameworks, thus opening attractive prospects for the synthesis of complex adaptive systems of practical interest / Doutorado / Engenharia de Computação / Doutor em Engenharia Elétrica

Orientadores: João Marcos Travassos Romano, Romis Ribeiro de Faissol Attux / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Eletrica e de Computação / Made available in DSpace on 2018-08-12T15:14:54Z (GMT). No. of bitstreams: 1 Dias_TiagoMacedo_M.pdf: 3219855 bytes, checksum: 5572e53d65cb457f420e78b3150dd6ee (MD5) Previous issue date: 2008 / Resumo: Esta dissertação se propõe a estudar um novo método para separação cega de fontes baseado no modelo Post-Nonlinear, que une uma ferramenta de busca global baseada em computação bioinspirada a uma etapa de busca local conduzida pelo algoritmo FastICA. A idéia subjacente à proposta é procurar obter soluções precisas e eficientes usando de maneira parcimoniosa os recursos computacionais disponíveis. A nova proposta foi testada em diferentes cenários, e, em todos os casos, estabeleceram-se comparações com uma abordagem alternativa, cujo passo de otimização não inclui o estágio de busca local (ou "memética"). Os resultados obtidos por meio de simulações indicam que um bom compromisso entre desempenho e custo computacional foi, de fato, atingido. / Resumo: Esta dissertação se propõe a estudar um novo método para separação cega de fontes baseado no modelo Post-Nonlinear, que une uma ferramenta de busca global baseada em computação bioinspirada a uma etapa de busca local conduzida pelo algoritmo FastICA. A idéia subjacente à proposta é procurar obter soluções precisas e eficientes usando de maneira parcimoniosa os recursos computacionais disponíveis. A nova proposta foi testada em diferentes cenários, e, em todos os casos, estabeleceram-se comparações com uma abordagem alternativa, cujo passo de otimização não inclui o estágio de busca local (ou "memética"). Os resultados obtidos por meio de simulações indicam que um bom compromisso entre desempenho e custo computacional foi, de fato, atingido. / Abstract: This work deals with a new method for source separation of Post-Nonlinear mixtures that brings together an evolutionary-based global search and a local search step based on the FastICA algorithm. The rationale of the proposal is to attempt to obtain efficient and precise solutions using with parsimony the available computational resources. The new proposal was tested in different scenarios and, in all cases, we attempted to establish grounds for comparison with an alternative approach whose optimization step does not include the local (memetic) search stage. Simulation results indicate that a good tradeoff between performance and computational cost was indeed reached. / Abstract: This work deals with a new method for source separation of Post-Nonlinear mixtures that brings together an evolutionary-based global search and a local search step based on the FastICA algorithm. The rationale of the proposal is to attempt to obtain efficient and precise solutions using with parsimony the available computational resources. The new proposal was tested in different scenarios and, in all cases, we attempted to establish grounds for comparison with an alternative approach whose optimization step does not include the local (memetic) search stage. Simulation results indicate that a good tradeoff between performance and computational cost was indeed reached. / Mestrado / Telecomunicações e Telemática / Mestre em Engenharia Elétrica

Made available in DSpace on 2016-03-15T19:37:43Z (GMT). No. of bitstreams: 1 Luiz Antonio Carraro.pdf: 1226702 bytes, checksum: 3cef29694a4e26f233b0aae16da69cf0 (MD5) Previous issue date: 2012-02-16 / Universidade Presbiteriana Mackenzie / A container is a broadly used solution for the cargo storage to be transported between ports, playing a central role in international trade. Consequently, ships grew in size in order to maximize their container transportation capacity in each trip. Due to increasing demand, container terminals face the challenges of increasing their service capacity and optimizing the loading and unloading time of ships. Optimization problems, such as these, often present features that make it impossible to obtain closed analytical solutions, requiring iterative search procedures in high-dimensional spaces, or subject to a combinatorial explosion of possible solutions. This dissertation presents the proposal of a novel meta-heuristic based on the Clonal Selection Algorithm, named MRC, to minimize the number of reshuffles in operations involving piles of containers. The performance of the proposed model was evaluated through simulations and results comparison with those obtained by algorithms from the literature under the same test conditions. The results obtained show that MRC is competitive in terms of minimizing the need of reshuffles, besides presenting a reduced processing time compared with models of similar performance. / A utilização de contêineres é uma solução amplamente adotada para o armazenamento da carga a ser transportada entre portos, tornando-se de grande importância no comércio internacional e, consequentemente, navios cresceram de tamanho com o objetivo de transportar a maior quantidade possível de contêineres em cada viagem. Devido à crescente demanda, terminais de contêineres enfrentam os desafios de aumentar a sua capacidade de atendimento e otimizar os tempos de carregamento e descarregamento de navios. Problemas de otimização como estes geralmente apresentam características que inviabilizam a obtenção de soluções analíticas fechadas, requerendo processos iterativos de busca em espaços de dimensão muitas vezes elevada, ou ainda sujeitos a explosão combinatória de possíveis soluções. Esta dissertação apresenta a proposta de uma meta-heurística bioinspirada baseada no Algoritmo de Seleção Clonal para a minimização de rearranjos em operações que envolvem pilhas de contêineres, denominado MRC. O desempenho do algoritmo foi avaliado por meio de simulações e comparação dos resultados com os obtidos por algoritmos da literatura sob as mesmas condições de teste. Os resultados obtidos permitem concluir que o MRC possui resultados competitivos em termos de minimização de rearranjos, além de apresentar um tempo de processamento reduzido quando comparado aos modelos tradicionalmente empregados na solução desse tipo de problema.

Submitted by Renata Lopes (renatasil82@gmail.com) on 2017-04-25T15:55:49Z No. of bitstreams: 1 larafurtadobastos.pdf: 4369558 bytes, checksum: 7b36e77b964a5ec919c2c9967a654a03 (MD5) / Approved for entry into archive by Adriana Oliveira (adriana.oliveira@ufjf.edu.br) on 2017-04-26T12:06:02Z (GMT) No. of bitstreams: 1 larafurtadobastos.pdf: 4369558 bytes, checksum: 7b36e77b964a5ec919c2c9967a654a03 (MD5) / Made available in DSpace on 2017-04-26T12:06:02Z (GMT). No. of bitstreams: 1 larafurtadobastos.pdf: 4369558 bytes, checksum: 7b36e77b964a5ec919c2c9967a654a03 (MD5) Previous issue date: 2016-09-08 / O presente trabalho apresenta a adaptação e utilização de um algoritmo da área de inteligência artificial evolucionária, bioinspirado no sistema de ecolocalização de morcegos, para resolver o problema da localização global de robôs móveis em ambientes bidimensionais com mapas conhecidos. Sabe-se, por meio da literatura, que a localização de robôs baseada apenas em dedução via hodometria, do inglês deduced reckoning ou dead-reckoning, acumula diversos erros de origem estocástica, os quais não podem ser eliminados de maneira determinística, fazendo-se necessários métodos de filtragem estatística para a correta obtenção da localização. Dentre as diversas alternativas conhecidas para solucionar o problema de localização, escolheu-se o Método Recursivo de Monte Carlo, também denominado por Filtro de Partículas, para comparação com os resultados obtidos pelo algoritmo de morcego, por suas características multimodais e não-paramétricas, sendo este um algoritmo clássico na área de localização robótica. O algoritmo de morcegos, do inglês Bat Algorithm, é um método recursivo de otimização de estados de um sistema que se encontra num ambiente multimodal. É bioinspirado nos sistemas de ecolocalização encontradas em morcegos e outros animais na natureza. Nos resultados de comparação entre ambos os métodos, a técnica proposta demonstrou melhores resultados tanto para o erro entre a localização real e a estimada pelos métodos quanto para o número de iterações necessárias para alcançar a solução e, consequentemente, o tempo de convergência do algoritmo. Para o desenvolvimento deste trabalho, utilizou-se o programa Matlab R integrado com a plataforma ROS, juntamente com o robô móvel terrestre Pioneer P3-DX para os resultados simulados e reais. / This work presents the adaptation and use an algorithm from evolutionary artificial intelligence area, bioinspired in the echolocation system of bats to solve the problem of global location for mobile robots in two-dimensional environments with known maps. It is widely known in literature that the localization of robots based only on deduced reckoning accumulates many stochastic errors, which cannot be eliminated deterministically, requesting statistical filtering methods to obtain the correct location. Among the various alternatives known to solve the problem of localization, we chose the Recursive Method of Monte Carlo, also kown as Particle Filter, for comparison purposes with the results obtained by the Bat Algorithm, because of its multimodal and nonparametric features, and alse because it is a classic algorithm in robotics localization area. The Bat Algorithm is a recursive optimization method of system states immerse in multimodal environments. It is bioinspired in the echolocation systems found in bats and other animals in nature. In comparison results between the two methods, the proposed technique showed the best results for both localization error and the number of iterations required to reach the solution, and consequently the algorithm convergence time. To develop this work, the Matlab software was used with the ROS framework along with the terrestrial mobile robot Pioneer P3-DX for simulated and real results.

Le sujet de la thèse concerne l’étude de l’inversion de valence dans des complexes FeIIFeIII induite par la déprotonation d’un ligand de FeII. L’intérêt de cette étude vient de ce que le processus considéré peut être décrit comme un transfert d’électron induit par un transfert de proton. Les transferts de protons et d’électrons sont au cœur de nombreuses réactions catalytiques ou biologiques et la compréhension des mécanismes de leur mise œuvre, séquentielle ou couplée, est un enjeu très actuel. La première partie de la thèse est consacrée à la caractérisation du premier système présentant cette propriété originale. Il est fondé sur un complexe binucléaire FeIIFeIII dont les deux ions Fe sont pontés par un dicarboxylate et un phénolate. Le FeIII est lié par un groupe bis-2-picolylamine et le FeII par un groupe similaire dans lequel une pyridine a été remplacée par une aniline. C’est la déprotonation de ce groupe aniline lié au FeII qui provoque l’inversion de valence, l’anilinate formé étant lié au FeIII. Le complexe aniline est isolé avec le groupe aniline en position -trans par rapport au phénolate pontant mais il possède la particularité de ne pas être stable en solution et de s’isomériser, le groupe aniline passant en position -cis par échange avec une pyridine. Le même phénomène est observé pour le complexe anilinate formé par déprotonation. Ce phénomène a été étudié en combinant les spectroscopies UV-visible, RMN du proton et Mössbauer et les caractéristiques thermodynamiques et cinétiques de l’isomérisation ont été déterminées. La relation entre le transfert d’électron et le transfert de proton a été étudiée par des techniques électrochimiques. Des études approfondies par cyclovoltamétrie et marquage isotopique ont montré que dans ce système les transferts d’électron et de proton sont concertés. La deuxième partie de la thèse est consacrée à l’étude des facteurs qui sont susceptibles d’influencer le transfert d’électron, c’est-à-dire les potentiels rédox des deux sites à Fe, et le transfert de proton, c’est-à-dire le pKa du ligand protique. Pour ce faire, de nouveaux complexes ont été préparés en modifiant soit le ligand protique, l’aniline étant remplacée par un benzimidazole, soit le groupe complexant le Fe, remplacement de la bis-2-picolylamine par la bis-(2-méthyl-N-méthylbenzimidazole)amine. Des complexes présentant ces modifications mais dépourvus du ligand acide ont été synthétisés pour étudier les effets de ces modifications sur les propriétés rédox des ions Fe. L’étude de l’influence des propriétés rédox a été menée dans un premier temps. La substitution du groupe complexant le FeIII n’a pas de conséquence importante au plan structural pour le complexe protoné qui existe toujours sous la forme de deux isomères. Par contre, après déprotonation un seul isomère existe. Les propriétés spectroscopiques sont peu altérées ce qui montre que la structure électronique du système n’est pas bouleversée. L’étude de l’influence des propriétés acides a été menée ensuite. Deux complexes ont été étudiés qui diffèrent par la nature du groupe complexant le FeIII. La substitution de l’aniline par le benzimidazole ne change pas de façon notable les propriétés structurales du système mais on note cependant que les valences des deux ions sont moins localisées. La déprotonation du benzimidazole est observée et conduit à un chromophore sensiblement différent du précédent illustrant les différences de ligand. L’étude électrochimique préliminaire révèle un comportement similaire au premier complexe étudié. / The thesis matter concerns the valence inversion in FeIIFeIII induced by deprotonation of a FeII ligand. This study is of strong interest owing to the fact this process can be described as an electron transfer induced by a proton transfer. Protons and electrons transfers play essential roles in numerous catalytic or biologic reactions and therefore understanding whether they occur in a sequential or concerted manner is presently a major endeavor. The first part of the thesis is devoted to the characterization of the first system possessing this original property. It is based on binuclear complex FeIIFeIII where the two Fe ions are bridged by a dicarboxylate and a phenoxide. The ferric ion is bound by a bis-2-picolylamine group and the ferrous ion by a similar group where a pyridine has been replaced by aniline. Deprotonation of this FeII bound aniline induces the valence inversion, the resulting anilide being bound to the FeIII ion. The aniline complex was isolated with the aniline in trans position with respect to the bridging phenoxide, but it is not stable in solution and isomerizes, the aniline group moving to a cis position upon exchange with a pyridine. The same phenomenon was observed for the anilide complex obtained through deprotonation. This phenomenon was studied by combining UV-visible, 1H-RMN and Mössbauer spectroscopies, and the thermodynamic and kinetic characteristics of the isomerization were determined. The link between the electron transfer and the proton transfer were studied by electrochemical techniques. Thorough studies by cyclic voltammetry and isotopic labeling showed that in this system the electron and proton transfers are concerted. The second section of the thesis was aimed at studying the factors susceptible to influence the electron transfer, namely the redox potentials of the two Fe sites, and the proton transfer, namely the pKa of the protic ligand. To achieve it, new complexes were prepared by modifying either the protic ligand, the aniline being replaced by a benzimidazole, or the Fe binding group, substitution of bis-2-picolylamine by bis-(2-methyl-N-methylbenzimidazole)amine. Model complexes incorporating these changes but deprived of the protic ligand were also obtained to assess their influence on the redox properties of the Fe ions. The study of the influence of redox properties was considered first. The substitution of the group complexing FeIII has not a strong influence on the structure of the protonated complex which still exists as two isomers. By contrast, after deprotonation a single isomer exists. The spectroscopic properties are mostly unchanged which shows that the electronic structure of the system is not altered significantly. The study of the influence of the acidicity was then conducted. Two complexes differing by the nature of the FeIII bound group were considered. Replacing aniline by benzimidazole does not change significantly the structural properties of the system, but the valences of the Fe ions are less localized than in the original complex. The deprotonation of benzimidazole occurs and leads to a chromophore that differs from the preceding, revealing the difference in ligands. However, a preliminary electrochemical study reveals a behavior similar to that of the original complex.