La tectonique moléculaire est une partie de la chimie supramoléculaire traitant de la formation d’architectures périodiques mono-, bi- et tridimensionnelles générées via l’auto-assemblage de briques moléculaires complémentaires nommées tectons. Ces derniers possèdent des sites de reconnaissance basés sur des interactions non-covalentes et réversibles. Les interactions largement utilisées sont les liaisons hydrogène et les interactions de coordination. Au cours de cette thèse, les sites de liaison H utilisés sont les nucléobases (thymine, adénine, cytosine, guanine) présentes dans l'ADN et l'ARN, qui ont été introduites en périphérie de différents sites de coordination, tels que les porphyrines, les dipyrrines, les pyridines et les terpyridines. Une bibliothèque de 25 nouveaux tectons à base de nucléobases a été synthétisée et caractérisée. De plus, les tectons ont été cristallisés pour étudier leur auto-assemblage à l'état solide. En présence de cations métalliques externes, les tectons conduisent à la formation de réseaux de coordination de topologies variées associant des liaisons H additionnelles entre les nucléobases. / Molecular tectonics is a field of supramolecular chemistry dealing with the formation of 1D, 2D and 3D molecular networks generated through the self-assembly processes between complementary building blocks (tectons). The latter offer complementary sites leading to recognition patterns via non-covalent and reversible interactions. The interactions widely used are hydrogen bonds and coordination interactions. During this thesis, the H-bonding sites used are the Nucleobases (Thymine, Adenine, Cytosine, Guanine) found in the DNA and RNA, which were introduced to different coordination sites, such as porphyrins, dipyrrins, pyridines and terpyridines. A library of 25 new tectons based on nucleobases were synthesized and characterized. Furthermore, the tectons were crystalized to study their self-assembly in the solid state. In the presence of external metal cations, the tectons lead to the formation of coordination and H-bonded networks of various topology via the self-assembly of nucleobases together with the formation of coordination bonds.

Développée il y a vingt ans par le professeur Grätzel, la technologie des cellules solaires à colorant constitue une alternative intéressante aux panneaux solaires à base de silicium communément commercialisés. Contrairement aux cellules photovoltaïques conventionnelles, le fonctionnement de ces dispositifs repose sur un principe inspiré de la photosynthèse naturelle. En effet, basés sur la sensibilisation de l’oxyde de titane par un colorant absorbant la lumière du soleil à l’instar de la chlorophylle chez les plantes, ces dispositifs permettent d’atteindre des rendements de conversion de l’énergie solaire en électricité de plus de 10% pour des coûts de production relativement bas. Ces travaux de thèse concernent la synthèse de nouveaux complexes de ruthénium porteurs de ligands terpyridines. Les ligands terpyridines ont été préparés par une méthode simple et douce. Une nouvelle voie de synthèse du ligand 4,4’,4’’-tricarboxy-2,2’ :6’,2’’-terpyridine (H3tcterpy) a été développée et comparée à la voie initiale en utilisant les critères de la chimie verte. Les complexes obtenus à partir de ces ligands ont été étudiés par spectroscopie d’absorption UV-visible, d’émission et par électrochimie afin de déterminer leur réponse spectrale ainsi que leurs propriétés énergétiques. Certains colorants ont été testés au sein de cellules photovoltaïques atteignant des performances allant jusqu’à 5,57% de rendement de conversion de l’énergie solaire en électricité. / Developed twenty years ago by Prof Grätzel, Dye sensitized solar cells are an interesting alternative to the commonly commercialized silicon based solar panels. Unlike conventional solar cells, the operation principle of these devices is based from natural photosynthesis. Indeed, based on the sensitization of titanium dioxide by a dye that absorbs solar light such as chlorophyll from plants, these devices can reach solar energy to electricity conversion yield above 10% with low production costs. This PhD project deals with the synthesis of new ruthenium complexes bearing terpyridine ligands. Terpyridine ligands have been prepared by a straightforward and mild method. A new route has been developed for the synthesis of 4,4’,4’’-tricarboxy-2,2’ :6’,2’’-terpyridine (H3tcterpy) and compared to the initial pathway using green chemistry criteria. The complexes obtained from these ligands have been studied by UV-visible and emission spectroscopies and electrochemistry with a view to determine their spectral responses and their energetic properties. Some of these dyes have been tested in dye sensitized solar cells, reaching solar energy conversion to electricity yields up to 5.57%.

Ce mémoire est consacré à l'élaboration, au greffage chimique de macrocycles azotés sur des surfaces, le développement des procédés d'élaboration de surfaces sensibles aux ions, l'évaluation de leurs propriétés et la réalisation de prototypes de capteurs chimiques sensibles aux ions. Les macrocycles azotés sont des cyclames sensibles aux ions de métaux de transition et des terpyridines sensibles aux lanthanides. Un capteur sensible à l'ion Fer (III) est réalisé par fonctionnalisation d'un ISFET et de structures de nitrure de silicium/silicium au moyen du greffage de macrocycles azotés de type cyclames sur la surface du dispositif. Un agent de couplage poly(méthylhydrosiloxane) (PMHS) permet cette immobilisation avec une grande efficacité. L'immobilisation d'un dérivé du cyclame (naphtyl-cyclam) sur des surfaces d'or a permis la préparation de capteurs chimiques sensibles aux ions. Les molécules de cyclame ont été déposées sur des électrodes en or par des interactions fortes entre le groupe de naphtyle et la surface d'or. Le film obtenu a été caractérisé en termes de composition, morphologie et propriétés électriques. La conductivité protonique du film naphtyl-cyclam a été mise en évidence par la spectroscopie d'impédance électrochimique (EIS) et la voltampérométrie cyclique (CV). Nous avons montré que l'immobilisation de dérivé de phényl-terpyridine sur des surfaces d'or a permis la préparation des capteurs chimiques sensibles aux ions Gadolinium (III). Les molécules de terpyridine ont été auto-assemblées sur des électrodes en or par des interactions fortes (greffage chimique) avec groupement thiol terminal. Les propriétés électriques de ces interfaces films sensibles/électrolyte sont décrites et des modèles théoriques sont proposés d'après les résultats expérimentaux obtenus par la spectroscopie d'impédance électrochimique / This dissertation is devoted to the elaboration, the chemical grafting of aminated macrocycles on surfaces, the development of elaboration processes of surfaces sensitive to the ions, the evaluation of their properties and the fabrication of prototypes of chemical sensors sensitive to the ions. The aminated macrocycles are cyclames, sensitive to transition metal ions and terpyridines sensitive to lanthanides. A chemical sensor sensitive to iron (III) ion is fabricated by means of the functionalization of an ISFET and of silicon nitride/silicon structures through grafting of aminated macrocycles of the cyclam type on to the surface of the device. The coupling agent poly(methylhydrosiloxane) (PMHS) allows such an immobilization with a high efficiency. The immobilization of a derivative of cyclam (naphtyl-cyclam) on gold surfaces allowed the preparation of chemical sensors sensitive to the ions. The molecule of cyclam was deposited on gold electrodes by strong interactions between the naphtyl group and the gold surface. The film obtained was characterized in terms of composition, morphology and electrical properties. The proton conductivity of the N-MNC film was brought out, for the first time, by electrochemical impedance spectroscopy (EIS) and by cyclic voltammetry (CV). We showed that the immobilization of the phenyl-terpyridine derived on gold surfaces allowed the preparation of the chemical sensors sensitive to gadolinium (III) ions. The molecules of terpyridine were self-assembled on gold electrodes by strong interactions (chemical grafting) with a final thiol group. The electrical properties of these sensitive films/electrolyte are described and theoretical models are proposed from the experimental results obtained by the electrochemical impedance spectroscopy

A química supramolecular representa o caminho mais promissor na rota de desenvolvimento da nanotecnologia devido à maneira especial com que diferentes moléculas interagem, trocando informações e criando estruturas organizadas. Esta tese pretende contribuir para este campo de pesquisa, através do estudo de três derivados terpiridínicos funcionalizados e seus complexos de ferro(II): 4\'-(3- tienil)- 2,2\':6\',2\'\'-terpiridina (titpy), [Fe(titpy)2]2+; 4\'-(4\'-(fenil)- 2,2\':6\',2\'\'-terpiridina (phtpy), [Fe(phtpy)2]2+ e 4\'-(4-bromo-fenil)-2,2\':6\',2\'\'-terpiridina (Br-phtpy), [Fe(Brphtpy)2]2+. A investigação desses complexos foi realizada por métodos espectroscópicos, físico-químicos e computacionais. As propriedades dos complexos sintetizados foram exploradas empregando o conceito de química supramolecular, através da interação dos mesmos com β-ciclodextrina, matriz de gel de pentóxido de vanádio e nanopartículas de ouro. Os novos materiais gerados apresentaram características que tornam possível a sua aplicação em diferentes áreas como: dosimetria UV-Vís, materiais para baterias e armazenamento de cargas e nanoestruturas organizadas. / Supramolecular chemistry is the most promising path on the development of nanotechnology. This is due to the special way that different molecules interact, exchanging information and generating organized structures. This PhD thesis intends to contribute in the supramolecular research field, with the study of three functionalized terpyridines derivates and the correlated iron(II) complexes: 4\'-(3-thienyl)-2,2\':6\',2\'\'-terpyridine, (titpy), [Fe(titpy)2]2+; 4\'-(4\'-(phenyl)- 2,2\':6\',2\'\'-terpirydine (phtpy), [Fe(phtpy)2]2+ and 4\'-(4-bromophenyl)-2,2\':6\',2\'\'- terpirydine (Br-phtpy), [Fe(Br-phtpy)2]2+. The investigations of the prepared compounds were done by spectroscopy, physicochemical and computational methods. The properties of the synthesized complexes were exploited in the supramolecular chemistry sense by the interactions of those compounds with α-cyclodextrin, vanadium pentoxide gel matrix and gold nanoparticles. The originated materials presented features that make possible the employment of them in distinct areas such: UV-Vis dosimeter, batteries and charge storage, and organized nanostructures

A química supramolecular representa o caminho mais promissor na rota de desenvolvimento da nanotecnologia devido à maneira especial com que diferentes moléculas interagem, trocando informações e criando estruturas organizadas. Esta tese pretende contribuir para este campo de pesquisa, através do estudo de três derivados terpiridínicos funcionalizados e seus complexos de ferro(II): 4\'-(3- tienil)- 2,2\':6\',2\'\'-terpiridina (titpy), [Fe(titpy)2]2+; 4\'-(4\'-(fenil)- 2,2\':6\',2\'\'-terpiridina (phtpy), [Fe(phtpy)2]2+ e 4\'-(4-bromo-fenil)-2,2\':6\',2\'\'-terpiridina (Br-phtpy), [Fe(Brphtpy)2]2+. A investigação desses complexos foi realizada por métodos espectroscópicos, físico-químicos e computacionais. As propriedades dos complexos sintetizados foram exploradas empregando o conceito de química supramolecular, através da interação dos mesmos com β-ciclodextrina, matriz de gel de pentóxido de vanádio e nanopartículas de ouro. Os novos materiais gerados apresentaram características que tornam possível a sua aplicação em diferentes áreas como: dosimetria UV-Vís, materiais para baterias e armazenamento de cargas e nanoestruturas organizadas. / Supramolecular chemistry is the most promising path on the development of nanotechnology. This is due to the special way that different molecules interact, exchanging information and generating organized structures. This PhD thesis intends to contribute in the supramolecular research field, with the study of three functionalized terpyridines derivates and the correlated iron(II) complexes: 4\'-(3-thienyl)-2,2\':6\',2\'\'-terpyridine, (titpy), [Fe(titpy)2]2+; 4\'-(4\'-(phenyl)- 2,2\':6\',2\'\'-terpirydine (phtpy), [Fe(phtpy)2]2+ and 4\'-(4-bromophenyl)-2,2\':6\',2\'\'- terpirydine (Br-phtpy), [Fe(Br-phtpy)2]2+. The investigations of the prepared compounds were done by spectroscopy, physicochemical and computational methods. The properties of the synthesized complexes were exploited in the supramolecular chemistry sense by the interactions of those compounds with α-cyclodextrin, vanadium pentoxide gel matrix and gold nanoparticles. The originated materials presented features that make possible the employment of them in distinct areas such: UV-Vis dosimeter, batteries and charge storage, and organized nanostructures