A series of kinetically stable chiral lanthanide complexes has been developed, with a view to developing responsive probes for use in analysis and in seeking chiral complexes exhibiting selectivity in their interaction with nucleic acids. Firstly a pH sensitive complex has been modified with the aim of tuning the pH range to which it responds to the physiologically useful regime. The synthesis was undertaken of relatively lipophilic 6-butylphenanthridinyl complexes. Their photophysical behaviour was investigated by absorbance and luminescence spectroscopy and the modulation of their emission examined in the pH range 4.5 to 7.5.In addition to their luminescent properties, enantiomerically pure chiral lanthanide complexes permit chiroptical techniques to be used, allowing their interactions with other chiral species to be addressed (e.g. nucleic acids, oligonucleotides).The first series of enantiopure lanthanide complexes has been devised that show several interesting features in binding to oligonucleotides and nucleic acids. These macrocyclic tris-and tetra-amide lanthanide (Eu, Tb or Yb) complexes contain an N-alkyl phenanthridinium unit that allows intercalation between the base pairs of the DNA. Their binding to [(AT)(_6)](_2), [(CG)(_6)](_2) and CT-DNA was monitored by changes in the ligand and metal based luminescence, and in the characteristic CD bands of the oligonucleotides. Binding affinities were assessed using intrinsic methods and the McGhee-von Hippel analysis. Marked differences have been observed in the binding of Eu and Yb complexes as a function of the A and Δ helicity of the complexes, which is itself determined by the configuration of the remote amide substituents. Binding of the A-Eu complex was over 50 times stronger to [(CG)(_6)](_2) compared to [(AT)(_6)](_2), while the left handed Δ-Yb complex showed a different pattern of selectivity. In the europium complex of a related heptadentate tris-amide ligand, the coordination of a DNA phosphate group to the lanthanide centre was suggested by emission and lifetime changes. Another series of chiral tetraamide complexes linked to the 6 position of the phenanthridine moiety was synthesised and studied. An additional stereogenic centre at carbon, alpha to the phenanthridine group was introduced with the aim of tuning the selectivity of binding. A set of four diastereoisomeric ligands was separated and their lanthanide complexes characterised. The binding of their Eu and Yb complexes was evaluated and differences between Eu and Yb complexes persisted. The additional chiral centre did not appear to modify the binding affinity of this series of complexes. Finally, a series of 6-phenanthridinyl complexes was investigated in which the phenanthridine N atom was directly bound to the lanthanide centre. Their affinity for DNA was found to be relatively low, which may be related to their rigid structure.

Au cours de ce travail de doctorat, nous avons d'abord étudié un aspect fondamental de la chiralité au niveau moléculaire visant à observer des différences d'énergie entre deux énantiomères provenant d'effets de violation de la parité (PV). Nous avons en particulier examiné les complexes oxorhénium chiraux dont les deux énantiomères présentent théoriquement des énergies d'absorption infrarouge différentes. Leur propriétés chiroptiques, en particulier leur dichroïsme circulaire vibrationnel (VCD), ont été examinées. D'autres complexes métalliques chiraux comme des complexes de platine portant un carbone asymétrique fluoré ont été préparés. Par ailleurs, nous avons étudié la chiralité hélicoïdale provenant de la fusion en ortho de plusieurs cycles aromatiques. Ainsi, des hélicènes portant des fonctionnalités bi-pyridines ont été synthétisés et ont montré des propriétés photophysiques et chiroptiques intéressantes. La présence d'unité chélatantes de type N^N’ ou N-C nous a permis d'étudier l'influence de la coordination de divers métaux de transition (Re(I) et Pt(II)) sur les propriétés et de concevoir de nouveaux commutateurs chiroptiques acido-basiques. / In this PhD work, we first investigated a fundamental aspect of chirality at the molecular level aiming to determine the parity violation (PV) energy difference between two enantiomers. We focused on chiral oxorhenium complexes for which the two corresponding enantiomers show theoretically different infrared absorption energies. Their chiroptical properties and especially their vibrational circular dichroism (VCD) were examined. Other chiral metal complexes such as platinum complexes bearing an asymmetric fluorinated carbon have also been prepared. Furthermore, we have investigated the helical chirality derived from the skew shape of ortho-fused aromatic ring. Indeed, helicenes bearing 2,2’-bipyridine functionalities were synthesized and they showed interesting photophysical and chiroptical properties. The presence of N^N’ or N-C chelating moieties enabled us to study the coordination effect of different transition metals (Re(I) and Pt(II)) on their properties and to conceive new acid-base triggered chiroptical switches.

Ce travail de thèse est dédié au développement des deux familles de complexes chiraux binaphtolates de terres rares et leur application en catalyse asymétrique dans les réactions d’addition de Michael, de Henry, de Strecker et d’hydroalkoxylation. La préparation d’une nouvelle famille de complexes chiraux bisbinaphtolates de terres rares a été optimisée. Ces nouveaux complexes ont été entièrement caractérisés grâce à des analyses RMN, IR, de spectroscopie de masse et des études de DRX de monocristaux isolés. Après une étude de stabilité, nous avons pu montrer que ces nouveaux complexes de terres rares peuvent être pesés à l’air libre et utilisés dans des réactions asymétriques sans dégazage des réactifs ni des solvants. Les comportements catalytiques de ces nouveaux complexes hétérobimétalliques ont été étudiés en détail dans des réactions énantiosélectives de Henry, de Strecker et d’addition de Michael. Une température d’isoinversion et un effet non linéaire ont notamment été mis en évidence dans la réaction d’addition de Michael de malonates sur des énones conduisant à des produits énantioenrichis avec des excès énantiomériques allant jusqu’à 83%. Une seconde famille de complexes monobinaphtolate monoalkyl de terres rares a été synthétisée et complètement caractérisée. Une structure DRX de ce type de complexe a pu être obtenue pour la première fois. Ces complexes ont été évalués dans des réactions de Strecker et d’hydroalkoxylation. Concernant cette dernière, la sélectivité a tout d’abord été étudiée avec ces complexes dans le cas des allènes et un mécanisme a pu être proposé. D’autre part, les premiers exemples d’hydroalkoxylation asymétrique d’alcènes, catalysés par ces complexes monobinaphtolate monoalkyl de terres rares, ont pu être décrits. / This thesis is mainly devoted to the development of two families of rare earths chiral binaphtolate complex and their application in asymmetric catalysis such as Michael addition, Henry reaction, Strecker reaction and hydroalkoxylation reaction. At first, the preparation of a new family of rare earth bisbinaphtolate complexes has been optimized with complete characterizations including NMR, IR, mass spectroscopy and XRD studies on isolated single crystals. These new rare earths complexes are relative stable which can be used under air condition. The catalytic behavior of these new heterobimetallic complexes have been studied in detail: an isoinversion temperature was determined and the nonlinear effect was observed for asymmetric Michael additions of malonates on enones wich lead products with enantiomeric excess up to 83%. Secondly, a family of rare earth monobinaphtolate monoalkyl complexs has been synthesized and characterized. The first XRD structure of this family of complex was obtained. Steric substitutions of binaphtolate ligands on position 3,3’ have been proven to be essential for the formation of these complex. The selectivity of reaction of hydroalkoxylation of allene was studied with a proposed mechanism. First examples of asymmetric hydroalkoxylation of alkene catalyzed by rare earth complexes have been achieved by our rare earth monoalkyl monobinaphtolate complex.