Several new late transition metal complexes containing P-O and P-N ligands derived from 2-dicyclohexylphosphinoacetaldehyde were synthesized. A facile one-pot template method is used for the synthesis of P-N complexes, where the phosphine aldehyde and amine can undergo a condensation reaction to form a phosphine-imine metal complex in the presence of a metal precursor. Metal complexes with phosphino-enolate, imine, and oxime ligands are synthesized. Ni(II), Pt(II), Rh(I) and Ir(I) metal centres were investigated. The Rh(I) and Ir(I) complexes contain a 1,5-cyclooctadiene ligand, thus resembling Crabtree’s hydrogenation catalyst [Ir(COD)(py)(PCy3)][PF6]. These complexes are also active catalysts for olefin hydrogenation. Furthermore, the synthesis of a new chiral amine functionalized NHC ligand is explored, which has potential applications as a ligand in the metal-catalyzed enantioselective hydrogenation of polar bonds. This ligand is inspired by previous achiral hydrogenation catalysts reported by Morris et al. that displayed high activity for a variety of unsaturated substrates.

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Recent advancements in supramolecular chemistry have given a wealth of strongly binding host-guest combinations. However, the deployment of these systems into meaningful constructs has been hindered due to difficulty of synthesis or to the lack of functionality in one or both components. Systems caught in this trap were the pyridyl cryptands of dibenzo-30-crown-10 and bis(m-phenylene)-32-crown-10 paired with paraquat. Exceptionally high association constants in the range of 105 to 106 have been observed for these systems, but their applications have been hindered. Easing the implementation of pyridyl cryptands based on dibenzo-30-crown-10 was made a priority. An efficient method for the synthesis of pyridyl cryptands based on dibenzo-30-crown-10 and bis(m-phenylene)-32-crown-10 made use of the salt pyridinium bis(trifluoromethane)sulfonamide (TFSI) as a template. Optimization of the pyridinium TFSI template allowed for cyclization yields as high as 89%, as well as without the use of a syringe pump. Addressing the concern of functionality, for pyridyl cryptands, chelidamic acid was targeted as a way to build in functionality. Using a chelidamic isopropyl ester, 20 new chelidamic precursors of varying functionality were synthesized. The chelidamic derivatives fell into six groups: potential covalent monomers, initiators, chain terminators, leaving groups, aryl halides and host-guest monomers. In an attempt to boost the association constants of pyridyl cryptands based on dibenzo-30-crown-10 with paraquat, alterations to the paraquat guest were explored. It was found that the association constants could be increased by nearly an order of magnitude. Tweaks to the paraquat included changing the counterion to TFSI, methyl groups to benzyl and allowing for access to more nonpolar solvents that were previously inaccessible, such as solvent change from DCM to acetone. Two new biscryptands and two new bisparaquat TFSI monomers were synthesized. Using these monomers supramolecular polymers were synthesized and characterized. Fibers of these polymers drawn from concentrated solutions were found to be flexible and one such polymer solution was found to have an upper log / log specific viscosity–concentration slope of 3.55, which is the theoretical maximum. Additionally, a biscryptand was used to produce a chain extended polymer. Using a fundamental understanding of host-guest chemistry, work was conducted on the synthesis of norbornene monomers and polymers with pendant imidazolium tethered by ethyleneoxy linkages to aid in the stabilization of the imidazolium cation. Through the use of ethyleneoxy linkages, the free anion content and conductivity was increased. Imidazolium monomer and polymer conductivities ranged up to nearly 10-4 S/cm. Furthermore, it was determined that as long as the ethyleneoxy spacer between the norbornene and imidazolium was two units or greater, similar properties were obtained for both the monomer and corresponding polymer. Expanding the work further, the imidazolium monomers were incorporated as a soft segment into a triblock copolymer to produce a single direction mechanical actuator. / Ph. D.

Les oxazolidinones sont des composés prometteurs pour des applications industrielles, mais aucune méthode ne convient à ce jour pour les produire à large échelle, à cause de l'utilisation de réactifs et de catalyseurs métalliques nocifs pour la santé et l'environnement. Une nouvelle méthode de synthèse de ces composés a donc été élaborée en utilisant des aminoalcools et du carbonate de diéthyle. Cette réaction est catalysée par un hydrogénocarbonate d'imidazolium biosourcé qui est produit par voie électrochimique afin de réduire son impact sur l'environnement.Cette méthode de synthèse d'oxazolidinones a ensuite été appliquée à la synthèse d'une oxazolidinone biosourcée. Pour cela, la synthèse d'un aminoalcool a été réalisée, et sa structure a été établie à partir de réactifs pouvant être issus de ressources renouvelables. La voie de synthèse a fait l'objet de modifications pour permettre la production de l'aminoalcool à plus grande échelle dans des conditions plus sûres.La seconde thématique de ces travaux porte sur les liquides ioniques, des sels liquides très peu volatils, couramment utilisés comme solvants. Ces composés sont généralement chers, ainsi, plutôt que de les éliminer à la fin de leur utilisation, il est plus intéressant de les recycler. Mais leur faible volatilité empêche leur recyclage par distillation, contrairement aux solvants organiques usuels. Il a ainsi été développé une première méthode électrochimique, économe en énergie, qui permet le recyclage de liquides ioniques biosourcés par la formation d'un hydrogénocarbonate d'imidazolium intermédiaire. Cette méthode a été comparée à d'autres procédés de recyclage grâce à une étude préliminaire du cycle de vie.Mots clés : oxazolidinone, aminoalcool, imidazolium, liquide ionique, biosourcé, recyclage, électrochimie, développement durable, écoconception, cycle de vie / Oxazolidinones are promising compounds for industrial applications, but nowadays there is not convenient method to produce them on large scale, because of the use of reactants and metallic catalysts harmful for health and environment. A new synthesis method of these compounds was thus elaborated using aminoalcohols and diethyl carbonate. This reaction is catalysed by a biobased imidazolium hydrogen carbonate which is produced by an electrochemical pathway in order to reduce its impact on the environment.This oxazolidinones synthesis method was then applied to the synthesis of a biobased oxazolidinone. To achieve this, an aminoalcohol synthesis was realised, and its structure was established from reactants that can come from renewable resources. The synthesis pathway was the object of modifications to permit the production of the aminoalcohol on a larger scale in safer conditions.The second thematic of these works is based on ionic liquids, very low volatile liquid salts, commonly used as solvents. These compounds are usually expensive, so, rather than to eliminate them at the end of their use, it is more interesting to recycle them. But their low volatility prevents their recycling by distillation, unlike common organic solvents. So, a first electrochemical method was developed, low energy consuming, permitting the recycling of biobased ionic liquids by the formation of an imidazolium hydrogen carbonate as intermediate. This method was compared with other recycling processes through a preliminary life cycle study.Keywords: oxazolidinone, aminoalcohol, imidazolium, ionic liquid, biobased, recycling, electrochemistry, sustainable development, eco-design, life cycle

La synthèse de nouveaux calixarènes fonctionnalisés par des groupes d’imidazolium occupe un grand intérêt qui se justifie par la facilité de fonctionnalisation des atomes d’azote de l’imidazole d’une part et d’autre part, par les propriétés de reconnaissance anionique liée à la charge positive délocalisée.Au cours de la première étape, nous avons effectué la fonctionnalisation des calixarènes au niveau de la partie basse en gardant le t-butyle au niveau de la partie haute. Dans un second temps, nous avons réalisé une substitution des atomes de brome par des dérivés d’imidazoles tel que 1-méthylimidazole, 2,4,6-triméthlimidazole, 2,6-diisopropylimidazole, l’imidazole et le benzimidazole afin de créer des ligands imidazolium, par la suite une réaction des sels d’imidazolium avec le nickelocène a conduit à la formation des complexes du NiCp. Dans une dernière étape, nous avons déterminé les propriétés complexantes des dérivés d’imidazolium vis-à-vis des anions organiques et inorganiques. / The synthesis of new calixarenes functionalized with groups imidazolium occupies a large interest, which is justified by the ease of functionalization of the nitrogen atoms of the imidazole on the one hand and on the other hand, by the anionic recognition properties related the delocalized positive charge.During the first step, we conducted the functionalisation of calixarenes at the lower part bearing the t-butyl at the top. Secondly, we made a substitution of bromine atoms by imidazole derivatives such as 1-methylimidazole, 2,4,6-triméthlimidazole, 2.6-diisopropylimidazole, imidazole and benzimidazole to create imidazolium ligands, subsequently a reaction imidazolium salts with nickelocene led to the formation of complexes NiCp.In a last step, we determined the complexing properties of imidazolium derivatives vis-à-vis organic and inorganic anions.

La détection de rayonnements ionisants - notamment les neutrons de basse énergie qui sont la signature de matériaux fissibles - est un enjeu majeur pour des applications duales civiles et militaires. La raréfaction de l’hélium 3 indispensable à la production de détecteur nécessite la découverte et la mise au point d’alternative fiable. Le développement de prototypes de détecteurs pour la caractérisation de neutrons permet de répondre aux risques d’accidents technologiques et de terrorisme. Mais ils permettent également l’amélioration de l’analyse de radiations ionisantes en recherche fondamentale. Une approche convergente de la synthèse des matériaux salins luminescents permet d’adresser à la fois la détection et la discrimination de rayonnements ionisants mais également de développer de nouveaux matériaux pour la détection de petites molécules en phase gazeuse. Les matériaux ioniques à base de sels d’imidazolium présentent des propriétés physiques remarquable tout en ayant une structure chimique malléable à façon. Ce projet vise à explorer de nouvelles méthodes pour la synthèse de sels d’imidazolium luminescents et leurs propriétés en détection. / Detector of ionizing radiation is a key challenge for both civil and military applications. New prototype of ionizing radiation discrimination helps us against technological accident and terrorism act. For instance, neutron of low energy is sign of fissile material. However current detectors require helium 3 which is scarce resource. Thus, a sustainable alternative has to be found. A convergent approach to synthesis active luminescent salt materials cope both. It identities and discriminate ionizing radiation. Especially for small cell in gas phase, this approach allows to develop new material to detect them. Based on imidazolium salt, ionic material has remarkable property with the benefit of being scalable.This project aims to explore new synthesis methods of luminescent imidazolium and their properties to identify ionizing radiation characteristic.