Polyarene dendrimers are composed entirely of aromatic rings and are of interest as they possess rigid and shape-persistent structures, which have potential applications in materials chemistry and as scaffold for functional molecules. This thesis describes the synthesis and characterisation of a number of new polyarene dendrimers containing pentaphenylbenzene-like (pentaaryl dendrimers) and hexaphenylbenzene-like (hexaaryl dendrimers) branching units which are capable of focal and peripheral expansions. These structures are based on terminal and internal 1,3-dialkyne cores, onto which two polyaryl sections were introduced via Diels-Alder reaction. These compounds possess inherent axial chirality as a result of the dialkyne position on the core, and a range of differently substituted polyaryl units which result in further chiral axes. Several crystal structures of pentaryl dendrimers were obtained, with these crystallising either as meso conformers or conformers with C2 symmetry. Introduction of a chiral auxiliary onto the central aromatic ring of these dendrimers provided evidence of the atropisomers in solution. These were studied via VT 13C NMR, revealing fast rotation and an energy barrier of about 66 kJ mol-1. The presence of additional aromatic rings on a hexaaryl dendrimer enabled observation of atropisomerism in solution owing to the greater steric hindrance of rotation of its branching units about the chiral axes. Fluorine-containing analogues of these dendrimers were synthesised and subjected to conformational studies through 19F-19F Exchange Spectroscopy (EXSY). Qualitative and quantitative analysis of the spectra revealed the kinetic and thermodynamic parameters, showing that the energy barrier of rotation of these dendrimers was within the range of 75-80 kJ mol-1, which was sufficient for spectroscopic observation but not for physical separation. Polyaryls with symmetry or lacking symmetry have been synthesised. The lack of symmetry was achieved by stepwise introduction of the polyaryl fragments. This demonstrates a route to polyaryls with sections possessing different structural features and thus potentially engineered properties and future chemical differentiations.

La résonance magnétique nucléaire est une technique de choix pour étudier la dynamique de l'échange dans des composés à portée thérapeutique. Cependant, les spectres acquis avec les méthodes 1D et 2D classiques présentent souvent des recouvrements importants, ce qui rend l'attribution de chaque espèce en échange difficile. Le développement méthodologique d'une approche pure shift permettrait donc d'améliorer la résolution de ces données. Au cours de cette thèse, nous avons effectué une série de développements méthodologiques des expériences de type EXSY dans lesquelles nous avons mis en œuvre différentes méthodes de découplage homonucléaire. En particulier, deux approches ont été testées: la méthode PSYCHE appliqué aux dimensions F1 et F2 des cartes EXSY, et la méthode Zangger-Sterk en F2. Ces approches ont toutes mené à une amélioration significative de la résolution qui nous a permis de caractériser les deux conformères s-cis/s-trans du Trandolapril. Nous avons également étudié l’intérêt de la technique d'échantillonnage non-uniforme (NUS) du signal pour réduire le temps d'analyse. Cette approche nous a permis de gagner en temps d'analyse, mais la présence d'artefacts à certaines températures suggère que d'autres développements seront encore nécessaires. Ces résultats ouvrent la voie vers une analyse plus fine du processus d’échange dans des composés présentant un spectre RMN complexe. / Nuclear magnetic resonance is a technique of choice for studying chemical exchange in therapeutic compounds. However, spectra acquired with standard 1D and 2D methods often show spectra with overlapping signals, which makes the assignment of each species difficult. Methodological development of a pure shift approach would therefore make it possible to improve the resolution of these data. During this thesis, we carried out a series of developments of the EXSY type experiments in which we implemented different homonuclear decoupling methods. Two approaches were tested: the PSYCHE method applied to the F1 and F2 dimensions of EXSY maps, and the Zangger-Sterk method in F2. These approaches all led to a significant resolution improvements allowing us to characterize the s-cis/ s-trans conformers in Trandolapril. We have also studied the interest of the non-uniform sampling (NUS) technique to reduce the analysis time. This approach allowed us to accelerate the experiment, but the presence of artifacts at various temperatures suggests that further developments will still be needed. These results pave the way for more analysis of the exchange process in compounds with complex NMR spectrum.

Les zéolites sont des «tamis moléculaires» connus pour leurs nombreuses applications en adsorption, échange d'ions et catalyse. Dans cette thèse, nous nous sommes concentrés sur l'étude de quelques questions liées à la synthèse et à la post-synthèse de la zéolithe, qui ne sont pas encore résolues par d'autres techniques.La RMN a été l'outil principal dans ce travail, donnant accès à des informations structurales locales sur les nanocristaux même lorsque les techniques de diffraction trouvent leurs limites. Elle peut également être utilisée pour étudier la porosité en utilisant l'adsorption de molécules sondes, et en particulier, le xénon est connu comme une bonne molécule pour cet objectif. En effet, l'isotope 129Xe peut être hyperpolarisé pour augmenter la sensibilité de détection, et il présente une large plage de déplacement chimique en fonction du confinement et donc de la porosité du matériau étudié.(I) Dans la première étude, les étapes initiales de la cristallisation de nano-faujasite (FAU) ont été étudiées en utilisant la RMN classique (principalement par 29Si et 23Na MAS RMN) et la RMN avancée (129Xe). RMN HP). Il a été montré que la cristallisation commence à des stades de synthèse bien antérieurs à ceux observés par d'autres techniques classiques (XRD, SEM, adsorption de N2 ...). La première SBU semble être les prismes hexagonaux, avant les cages sodalite, qui forment rapidement un environnement confiné puis des supercages. De plus, il a été démontré par RMN 129Xe HP et 2D EXSY que la zéolithe nano-faujasite présente des cages sodalite ouvertes et une structure plus souple que dans la zéolite de type micro-faujasite.(ii) La seconde étude est une recherche sur les phénomènes de recristallisation survenant au cours du processus de hiérarchisation de la zéolithe et qui pourrait expliquer la distribution homogène des tailles de mésopores. Comme résultat remarquable, il a été montré dans ce travail que lors de la hiérarchisation de la zéolithe bêta avec le TPAOH, la recristallisation conduisait à la formation de minuscules particules de MFI, formées à la surface des mésopores (RMN 1H MAS, RMN 129Xe HP et 2D EXSY). / The zeolites are ‘molecular sieves’ known for their numerous applications in adsorption, ion exchange, and catalysis. In this thesis, we focused on the study of some questions related to zeolite synthesis and post-synthesis, which are not yet resolved by other techniques. NMR was the primary tool in this work, as it gives access to local structural information on nanocrystals even when diffraction techniques found their limits. NMR can also be used to study porosity using probe molecules adsorption, and in particular, xenon is known as a good molecule for this purpose. Indeed, the isotope 129Xe can be hyperpolarized to increase the detection sensitivity, and interestingly it presents a wide chemical shift range depending on its confinement and thus the porosity of studied material. Two studies are reported in this manuscript: (i) In the first study, the initial steps during the crystallization of nano-faujasite (FAU) type materials were investigated using classical NMR (mainly by 29Si and 23Na MAS NMR) and advanced NMR (129Xe HP NMR). It was shown that crystallization starts at much earlier synthesis stages than those observed by other classical techniques (XRD, SEM, N2 adsorption…). The first SBU seems to be the hexagonal prisms, prior to the sodalite cages, which rapidly form confined environment and then supercages. Moreover, it has been proved by 129Xe HP NMR and 2D EXSY that nano-faujasite zeolite presents opened sodalite cages and a more flexible structure than in micro-faujasite zeolite. (ii) The second study is an investigation on the recrystallization phenomena occurring during hierarchization process of zeolite and which could explain the homogenous distribution of the mesopore sizes. As a remarkable result, it has been shown in this work that during the hierarchization of beta zeolite with TPAOH, the recrystallization lead to the formation of tiny MFI particles, formed at the surface of the mesopores (1H MAS NMR, 129Xe HP NMR and 2D EXSY).

Abstract The present thesis exploits advanced liquid and gas NMR methods for the characterization of various interesting materials. The methods used to study the structural properties of thermally modified wood, ionic liquids, cements, shales, and porous organic cages include MRI, NMR cryoporometry, Laplace NMR, multidimensional Laplace NMR, as well as ¹²⁹Xe and ¹⁹F NMR. The commonality factor in all the studies is the usage of either inherent or introduced liquid or gas molecules to probe the topical materials. The MRI method was utilized to visualize the water absorption phenomena in the thermally modified pine wood. High-resolution images made it possible to observe the spatial distribution of free water and the changes in the rate of absorption of water in wood samples modified at different temperatures. The images also helped to resolve the individual resin channels. T₂ maps enabled us to observe the changes in the relaxation values of free water in thermally modified wood as compared to their unmodified reference wood samples. The multidimensional Laplace NMR methods were exploited to study the structural and dynamical properties of a novel halogen-free, boron-based ionic liquid (hf-BIL). NMR self-diffusion (D) experiments showed the presence of two coexisting dynamic phases in hf-BIL. Multidimensional D − T₂ correlation experiments made it possible to determine the T₂ relaxation times of the slow and fast diffusing phases. T₂ − T₂ relaxation exchange measurements allowed quantifying the exchange rates of anions and cations between the phases. Moreover, the theoretical modeling of the experimental data revealed that the slow diffusing phase was composed of anion-cation aggregates, while the fast diffusing phase was comprised of free anions and cations. ¹²⁹Xe NMR analysis of the xenon adsorbed in the cements and shales helped us to determine their porous structures. The method exploits the high sensitivity of the chemical shift of ¹²⁹Xe to its local environment. The chemical shift value of ¹²⁹Xe enabled us to estimate the size of the mesopores in the cement samples. The exchange spectroscopy (EXSY) measurements were used to determine the exchange rates between the free gas and mesopores of the cement samples. ¹²⁹Xe NMR spectra of the shale samples provided information about pore sizes and paramagnetic compounds. ¹H NMR cryoporometry measurements of the shale samples immersed in acetonitrile made it possible to analyze the pore size distribution ranging from 10 to over 100 nm. Moreover, T₂ − T₂ exchange measurements helped us to quantify the exchange rates of acetonitrile in the shale samples. Xenon and SF₆ were used as internal reporters to gain versatile information on adsorption phenomena in the cage and window cavities of the crystalline porous organic cages. ¹²⁹Xe NMR analysis of the adsorbed xenon helped us to determine the diffusion coefficients and activation energy of diffusion as well as thermodynamic parameters. With the help of T₂ relaxation time values, it was possible to estimate the exchange rates between cage and window cavities. Chemical exchange saturation transfer (CEST) experiments resolved a window cavity site, which arises from crystal defects in porous organic cages. In addition, ¹⁹F NMR analysis made it possible to estimate the relaxation rates and diffusion coefficients of SF₆ gas in porous organic cages. Modelling of the T₁, T₂ and diffusion data confirmed that the cage to window exchange is the completely dominating mechanism for ¹²⁹Xe T₂ relaxation. T₁ relaxation is dominated by diffusion modulated dipole-dipole relaxation (DDinter) and chemical shift anisotropy (CSA) relaxation due to local cavity mobility. Whereas, in case of SF₆ T₂ data, the dominating mechanism is diffusion modulated dipole-dipole relaxation and for T₁ the local tumbling of SF₆ in cage cavity is the key dynamics behind the dipole-dipole and CSA mechanisms. / Original papers The original publications are not included in the electronic version of the dissertation. Javed, M. A., Kekkonen, P. M., Ahola, S., & Telkki, V.-V. (2015). Magnetic resonance imaging study of water absorption in thermally modified pine wood. Holzforschung, 69(7), 899–907. https://doi.org/10.1515/hf-2014-0183 Javed, M. A., Ahola, S., Håkansson, P., Mankinen, O., Aslam, M. K., Filippov, A., … Telkki, V.-V. (2017). Structure and dynamics elucidation of ionic liquids using multidimensional Laplace NMR. Chem. Commun., 53(80), 11056–11059. https://doi.org/10.1039/c7cc05493a http://jultika.oulu.fi/Record/nbnfi-fe2017102750335 Javed, M. A., Komulainen, S., Daigle, H., Zhang, B., Vaara, J., Zhou, B., & Telkki, V.-V. (2019). Determination of pore structures and dynamics of fluids in hydrated cements and natural shales by various ¹H and ¹²⁹Xe NMR methods. Microporous and Mesoporous Materials, 281, 66–74. https://doi.org/10.1016/j.micromeso.2019.02.034 http://jultika.oulu.fi/Record/nbnfi-fe2019041712678 Komulainen, S., Roukala, J., Zhivonitko, V. V., Javed, M. A., Chen, L., Holden, D., … Telkki, V.-V. (2017). Inside information on xenon adsorption in porous organic cages by NMR. Chemical Science, 8(8), 5721–5727. https://doi.org/10.1039/C7SC01990D http://jultika.oulu.fi/Record/nbnfi-fe201709288804 Håkansson, P., Javed, M. A., Komulainen, S., Chen, L., Holden, D., Hasell, T., … Telkki, V.-V. (2019). NMR relaxation and modelling study of the dynamics of SF₆ and Xe in porous organic cages. Manuscript.

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