Submitted by Angela Maria de Oliveira (amolivei@uepg.br) on 2019-03-15T17:47:02Z No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) Michele_Mugnaine.pdf: 11968218 bytes, checksum: 5ba2af6a329e543934e520e416683d5c (MD5) / Made available in DSpace on 2019-03-15T17:47:02Z (GMT). No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) Michele_Mugnaine.pdf: 11968218 bytes, checksum: 5ba2af6a329e543934e520e416683d5c (MD5) Previous issue date: 2019-02-21 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / O mapa padrão não twist é um exemplo simples e geral de sistemas Hamiltonianos que violam a condição twist. Sua aplicação abrange fenômenos associados a plasmas, dinâmica celeste, guias de onda, aceleradores de partículas, entre outros. A presença de cadeias gêmeas e da curva shearless, neste mapa, tem uma grande influência sobre as barreiras presentes no espaço de fase e sobre o transporte observado através dele. Neste trabalho, fornecemos uma conexão entre os mecanismos de turnstiles e o cenário de intersecção entre variedades das cadeias gêmeas com o transporte no espaço de fase, uma situação ainda não completamente entendida em sistemas Hamiltonianos não twist. O alto transporte está relacionado com o cenário de intercrossing, com a proximidade dos pontos homoclínicos e heteroclínicos das duas cadeias e com os turnstiles agindo como um mecanismo de transporte, como uma passagem da trajetória de uma região a outra no espaço de fase. Já o transporte baixo é representado pelo cenário oposto, temos um cenário de intracrossing com uma distância maior entre os pontos de interseção e os turnstiles agindo como mecanismo de barreira de trajetórias. O mapa não twist é um mapa simétrico, sendo assim, não há uma direção preferencial para o transporte. Entretanto, a adição de uma nova perturbação na forma c sen(2πmx) é capaz de quebrar a simetria, para m par, e assim o transporte direcionado é um fenômeno possível. O mapa com esta nova perturbação é denominado mapa padrão não twist estendido e ele apresenta fenômenos interessantes como a quebra de simetria, transporte direcionado e a recuperação do cenário monotônico, cenário não observado no mapa não twist original. / The standard nontwist map is a simple and general example of Hamiltonian systems that does not satisfy the twist condition. The map applications cover phenomenons related to plasmas, celestial mechanics, wave guides, particle accelerators and other examples. The presence of twin islands chains and the shearless curve has a big influence over barriers in the phase space and, consequently, over the transport through the space. In this work, we provide a connection between turnstiles, the manifolds intersection scenario and the transport in the phase space. This connection is still not completely understood in non twist Hamiltonian systems. The high transport is associated to the intercrossing scenario and how the homoclinic and heteroclinic points from different islands chains are close to each other and how the turnstiles act like a transport mechanism. The turnstile is the gate or the barrier to the trajectories from one region of the phase space to another. The low transport is represented by the opposite scenario, the intracrossing scenario has a larger distance between the intersection points. In this case, the turnstiles act as a trapping mechanism. The standard nontwist map is a symmetric map, i.e, there is not a preferential direction for the trajectories to follow. However, the addition of a new perturbation with a shape as csin(2πmx) is able to break the symmetry, if m is even, and the directed transport is a possible phenomenon to exist in the phase space. The map with the new perturbation is called extended standard nontwist map and it features interested phenomenon as the symmetry breaking, directed transport and the recovery of the monotonic scenario, which is not present in the original nontwist map.

Soucieux de comprendre et de développer une ingénierie moléculaire, les scientifiques ont façonné et produit des objets nanométriques, apparentés à ceux qui nous sont familiers. Le travail présenté ici rassemble les stratégies de synthèse organique mises en œuvre dans la production de tourniquets moléculaires commutables. L'objectif est d'introduire un site catalytique et d'apprécier la modulation de l'activité en fonction de conditions contrôlables. Partant de synthèses multi-étapes optimisées, plusieurs familles ont été préparées, caractérisées et leur performance catalytique a été évaluée. Parallèlement, un intérêt s'est porté sur une question soulevée par la modulation de la cinétique de rotation dans de tels objets. Cette étude a mobilisé une activité de synthèse d'objets isomérisables, d'études RMN, et a été complétée d'un regard photo-physique et théorique. Avec la volonté de structurer les objets, une dernière étude a porté sur l'assemblage de réseaux de coordination construits sur des ligands photo-sensibles. / With a constant desire to understand and develop molecular engineering, scientists have conceived and produced a wealth of systems, similar to the ones we are confronted with everyday. In this work, organic synthesis strategies are presented for the preparation of switchable molecular turnstiles. The goal was to introduce catalytic sites and to follow their activity under controlled conditions. From multi-step and optimized routes, several families were synthesized, characterized and their catalytic activites were evaluated. In the meantime, interest was focused on the modulation of kinetics in such systems. Photo-isomerizable compounds were prepared and characterized by NMR, and later examined with photo-physics and theoretical approaches. Eager to build up organized objects, coordination networks were finally prepared from photo-sensitive ligands.

Les travaux décrits dans ce manuscrit s’intéressent au contrôle du mouvement moléculaire. Après une introduction dédiée à l’état de l’art des machines moléculaires, le premier chapitre s’intéresse à la conception de tourniquets moléculaires à base de complexes porphyriniques de P(V). Le mouvement moléculaire a pu être contrôlé de manière réversible soit par l’utilisation des sites de coordination présents à la périphérie du système soit par des variations de pH. Le deuxième chapitre s’intéresse aux propriétés photophysiques des porphyrines de P(V) obtenues et plus particulièrement à leur capacité à générer de l’oxygène singulet avec une application potentielle en Thérapie Photodynamique (PDT).Le troisième chapitre concerne l’élaboration d’un complexe contenant deux porphyrines de Zn(II) dont le mouvement relatif a pu être bloqué réversiblement par l’utilisation des positions axiales des cations métalliques. / The manuscript focuses on molecular machines and the control of their movement. Two different devices have been designed, synthetized and characterized. Moreover, a series of new potential photosensitizer was obtained.The introduction gives a general overview on molecular machines, reported during the past 20 years. The first chapter describes the synthesis of molecular turnstiles based on P(V) porphyrins. The molecular motion was controlled reversibly using either coordination chemistry or by changing the pH. The second part is dedicated to the study of the photophysical properties of P(V) porphyrins and especially their capacity to generate singlet oxygen under irradiation., making them potential photosensitizers that can be use in Photodynamic Therapy (PDT) or as catalyst. The third chapter is devoted to the study of a molecular break based on a Zn (II) porphyrin dimer. The control of the movement was performed using the coordination of a bidentate ligand in the axial position of the metal cations.

Thesis is focused on creation of an information system for a visitor center in Olomouc. This document describes whole lifecycle of that reservation system, including requirements specification, system design, its implementation and testing. Final system will be deployed in museum, where it will handle the control of turnstiles, ticket reservations and sales.

Le contrôle du mouvement à l’échelle d’une simple molécule est un sujet actuellement florissant et intensément exploré par des chimistes de tous horizons. Le travail présenté dans ce manuscrit s’inscrit dans ce cadre. La conception ainsi que l’étude en solution et à l’état cristallin de tourniquets moléculaires, espèces composées d’un rotor et d’un stator comportant plusieurs sites d’interaction, y sont décrites.Dans une première partie, la synthèse ainsi que le fonctionnement de tourniquets à charnière de Pt(II) sont décrits. La fermeture et l’ouverture de ces systèmes ainsi que les essais de passage d’une station à une autre y sont étudiés. Les sites d’interactions ont été variés sur le rotor et le stator, pour aboutir à des systèmes variant par la dynamique de leur comportement.Dans une seconde partie, une synthèse optimisée de tourniquets à charnière organique est décrite. Les états ouverts et fermés de ces tourniquets ont été caractérisés.Tous les processus décrits pour les tourniquets ont été étudiés par des études RMN mono- et bi-dimensionnelles en solution.Dans un dernier chapitre, des MM’OFs basés sur un tecton comportant un centre Pt(II) et deux sites coordinant de type pyridine sont exposés. Leur utilisation en tant que tecton organométallique avec divers centres métalliques conduit à la formation de réseaux hétérobimétalliques. Un ligand incluant deux centres Pt(II) et un centre Fe(II) entouré par deux terpyridines est décrit. / The control of intramolecular movements has been a topic of high interest for chemists over two decades. Investigations described in this PhD manuscript aim at the design and study, both in solution and in the crystalline state, of molecular turnstiles. These entities are composed of a rotor and a stator, each of these constituents equipped with recognition sites.In the first part, the synthesis and behavior of Pt(II)-based molecular turnstiles are described. The switching between their open and closed states and the migration process between stations are discussed. The recognition sites on both the stator and rotor have been varied, leading to different behaviors, particularly in terms of their dynamics.In solution, 1- and 2-D NMR have been used for the characterization of the dynamic processes.In the last chapter, the use of a Pt(II)-bispyridyl based tecton for the synthesis of MM’OFs is reported. The use of various metal salts as secondary center has led to the construction of networks varying by their geometry and dimensionality. A ligand including two Pt(II) and one Fe(II) complexed by two terpyridyl units is described.