Abstract This research work details a systematic study of the structure and function of supramolecular host-guest systems. Host-guest inclusion complexes were formed between β-Cyclodextrin (β-CD) and its copolymers (as hosts), with several types of guest molecules both in aqueous solution and the solid state. The research is divided into two themes; (1) structural characterization and dynamic properties of the inclusion compounds of β-CD with various guest systems in aqueous solution and the solid phase, and (2) heterogeneous adsorption and structural studies of β-CD based copolymers with various guest systems in aqueous solutions. The guest systems include alkyl and perfluoroalkyl carboxylates, perfluoroalkyl sulfonate, and p-nitrophenol (PNP) at variable experimental conditions. In the first theme (chapter 2-5), host-guest complexes in the solid state were prepared using dissolution and slow cool methods at variable host/guest mole ratios (i.e., 1:1 and 2:1). The complexes were further characterized using 19F/13C DP/MAS and CP/MAS solid-state NMR spectroscopy. The solution state complexes were prepared in D2O for structural characterization using 1H/19F NMR spectroscopy. The NMR studies were complemented using FT-IR, thermal analyses (DSC, and TGA), and powder X-ray diffraction (PXRD). Evidence for the formation of host-guest inclusion compounds (ICs) was provided using CP/MAS solids NMR spectroscopy and complexation-induced chemical shift (CIS) values of 1H/19F nuclei in aqueous solution. The β-CD/PFC ICs displayed variable guest geometry and hydration states as determined by the host-guest stoichiometry and the conformation of the guest. PFOA and SPFO form 1:1 and 2:1 ICs with β-CD, wherein the guest adopts a range of gauche and trans conformations, respectively. 1:1 host-guest complexes were concluded for short perfluorocarbon chains (i.e., PFBA) where the gauche conformation of the PFC guest in the bound state was favoured. In the second theme (chapters 6–8), β-CD based copolymers were used as host materials. The structural characterization of a soluble poly-CD material (known as HDI-1) revealed that the solution behaviour of such polymeric hosts are sensitive to the presence of guest compounds such as p-nitrophenol (PNP) (i.e. chemo-responsive), as well as temperature variations (i.e. thermo-responsive). The host-guest chemistry of the soluble poly-CD material, as studied by 2-D solution NMR and induced circular dichroism (ICD) spectroscopy, indicates that PNP was bound within the cavity sites of β-CD and the interstitial domains of the copolymer (cf. Scheme 1.6 and chapter 6). The observed responsive nature of such polymeric host materials to temperature variation and chemical potential resembles behaviour characteristic of ‘smart materials’. Herein, ‘smart materials’ refer to systems which are responsive to external stimuli (e.g. temperature and chemical). The adsorption properties of the soluble (HDI-1) and insoluble (HDI-3 and -6) poly-CD adsorbents with octyl and perfluorooctyl carboxylate and sulfonate anions were estimated using the Sips and BET models. The hydrocarbon (HC) and fluorocarbon (FC) anions form monolayer and multilayer structures at the surface of the polymeric adsorbents, respectively. The formation of layered structures was controlled by the relative hydrophobicity of the alkyl/perfluoroalkyl chains and their mutual miscibility with the adsorbent surface. Other factors include the inductive effects of the alkyl/perfluoroalkyl head groups and their interactions with aqueous solvent or dipolar domains of the adsorbent surface. The adsorbed species at the liquid-solid interface were characterized using FT-IR spectroscopy, thermal analyses, and contact angle.

Ce travail de thèse a pour objet la synthèse, la caractérisation et l’étude des propriétés de complexation de cages moléculaires riches en électrons, préparées selon une stratégie d’auto-assemblage dirigé par des métaux, ainsi que l’étude de leur aptitude à complexer ou libérer un substrat à l’aide d’un stimulus redox.Une présentation de la stratégie d’auto-assemblage dirigé par des métaux et de son efficacité pour l’élaboration de structures tridimensionnelles est d’abord proposée.Ce projet repose sur un travail préalable de synthèse de ligands riches en électrons, dérivés de l’unité tétrathiafulvalène (TTF) ou de son dérivé à système-pi étendu (ex TTF), motif dont les propriétés de donneurs pi sont bien établies. Plusieurs ligands tétra-topique sont ainsi été préparés et caractérisés.Les auto-assemblages discrets correspondant ont été obtenus par réaction avec divers complexes métalliques, donnant naissance à des cavités variées,contrôlées en termes de forme et de taille. Ces édifices ont été caractérisés par RMN (dont DOSY),spectrométrie de masse, le cas échéant par diffraction des rayons-X et leurs propriétés électrochimiques ont été étudiées par voltammétrie cyclique. Leur capacité à complexer des invités neutres ou ioniques a également été mise en évidence. Enfin, exploitant les caractéristiques géométriques et électroniques remarquables des dérivés à base ex TTF, l’aptitude de l’une des cages correspondantes à contrôler réversiblement le processus de libération/complexation d’un invité par oxydation/réduction chimique, a pu être démontrée. / This work is related to the synthesis and the characterization of electron-rich molecular cages, which are generated through a coordination-driven selfassembly strategy, as well as to the study of their ability to complex or release a substrate using a redox stimulus. A presentation of the metal-driven self-assembly methodology and of the corresponding efficiency in the preparation of three-dimensional structures is first proposed. This project is based on preliminary efforts in the design and the synthesis of electron-rich ligands, which are derived from the tetrathiafulvalene unit (TTF) or its piextended derivative (exTTF), whose pi-donating properties are well-established. Several tetratopic ligands were prepared and characterized. The corresponding discrete self-assemblies were obtained by reaction with various metal complexes, giving rise to various cavities whose shapes and sizes can be triggered. These structures were characterized by NMR (including DOSY), mass spectrometry, X-ray diffraction in some cases. Their electrochemical properties were studied by cyclic voltammetry. Their good binding properties for various neutral and ionic guests were also shown. Finally, exploiting the remarkable geometric and electronic features of exTTF derivatives, the ability of one of the corresponding cages to trigger reversibly the release/complexation process of a guest upon chemical oxidation/reduction, could be demonstrated

Synthesis of cyclodextrin derivatives for practical applications Abstract The first part of this PhD thesis is focused on the synthesis of a series of monosubstituted tetraalkylammonium cyclodextrin (CD) derivatives. The emphasis was placed on the possible applicability of the synthetic process to multigram or even industrial scale. Monotosylation of the native cyclodextrins (-, -, -) on the primary side of the macrocycle afforded the starting materials. Derivatives with one cationic group were prepared by the reaction with aqueous trimethylamine. The reaction of the mono-Ts-CD with neat N,N,N'-trimethylethane-1,2-diamine or N,N,N'-trimethylpropane-1,3-diamine and subsequent methylation led to derivatives with the substituent bearing two cationic groups (PEMEDA- and PEMPDA-β-CD). Analogs bearing a moiety with three tetraalkylammonium sites were synthesized by reaction of mono-Ts-CD with bis(3-aminopropyl)amine with subsequent methylation. 1,3-Dipolar cycloaddition of mono-6- azido--CD with diaminoacetylenes followed by methylation led to analogs with a avariable distance of the charged substituent from the CD core. Majority of the presented reactions are straightforward, relatively high-yielding and the workup does not require chromatographic steps. The second part of the work is dealing with the...