Tesi sul tema "Aimants à base de molécules"
Cita una fonte nei formati APA, MLA, Chicago, Harvard e in molti altri stili
Vedi i top-50 saggi (tesi di laurea o di dottorato) per l'attività di ricerca sul tema "Aimants à base de molécules".
Accanto a ogni fonte nell'elenco di riferimenti c'è un pulsante "Aggiungi alla bibliografia". Premilo e genereremo automaticamente la citazione bibliografica dell'opera scelta nello stile citazionale di cui hai bisogno: APA, MLA, Harvard, Chicago, Vancouver ecc.
Puoi anche scaricare il testo completo della pubblicazione scientifica nel formato .pdf e leggere online l'abstract (il sommario) dell'opera se è presente nei metadati.
Vedi le tesi di molte aree scientifiche e compila una bibliografia corretta.
Jung, Julie. "Étude ab initio de molécules aimants à base d'ions lanthanides". Thesis, Rennes 1, 2015. http://www.theses.fr/2015REN1S038/document.
Testo completoLanthanide ions have been used successfully in the synthesis of single molecule magnets for more than a decade. This particular class of molecules shows slow relaxation of their magnetization from purely molecular origin. This property come mainly from the strong single ion anisotropy of these ions, and from their high magnetic moment. In the case of complexes with more than one spin carrier (3d, 4f metal or organic radical), coupling interactions can arise. These are called magnetic exchange. In this framework, ab initio calculations are a useful tool for magneto-structural correlations
Long, Jérôme. "Assemblages supramoléculaires hétérotrimétalliques à base d'octacyanométallate : vers des molécules-aimants photo-commutables". Paris 6, 2009. http://www.theses.fr/2009PA066281.
Testo completoIasco, Olga. "Aimants moléculaires à base de clusters polymétalliques : synthèse, structures cristallines et étude des propriétés magnétiques". Phd thesis, Université Claude Bernard - Lyon I, 2011. http://tel.archives-ouvertes.fr/tel-00838606.
Testo completoEl, Rez Bahjat. "Contrôle de la stéréochimie du centre Ln dans des complexes base de Schiff 3d-4f : application à l'élaboration de molécules-aimants chirales". Thesis, Toulouse 3, 2015. http://www.theses.fr/2015TOU30002/document.
Testo completoThe research work described in this thesis deals with the design, the synthesis and magnetic property investigation of magnetic low dimensional molecular materials (i.e. single Molecule Magnets, SMM), especially in 3d-4f Schiff-base complexes, involving magnetically anisotropic lanthanide (Ln) metal centers in conjunction with chirality. The aim of this investigation was to provide an efficient access to enantiopure SMMs chiral at metal (Ln). We developed an original chemical approach that consists in introducing a chiral chelating diketonate ligand directly bonded to the Ln metal center. Thus transfer of chirality from chiral ligand to the coordination polyhedron of the metal center can be achieved. Deprotonated 3-trifluoroacetyl-camphor (Camph-) has been utilized as the chiral chelating ligand to synthesize several 3d-4f Schiff-base complexes, where two chiral anions are anchored on Ln ion rendering chiral coordination sphere around the rare-earth metal center. Depending on the enantiomer of the ligand employed in the synthesis, either Delta or LAmbda stereochemistry of the Ln polyhedron is obtained. This approach allowed synthesis of several families of enantiopurs SMMs chiral at Ln such as [LMe2Ni(H2O)Ln(camph)2(CF3SO3)] or [LMe2Zn(Cl)Ln(camph)2(MeOH)], where LMe2 = bicompartmental Schiff-base ligand. In each case, reaction with the R-(+) Camph ligand results in a Lambda stereochemistry, while a Delta stereochemistry is yielded upon reaction with the S-(-) Camph ligand. However, such a stereo-selectivity is not systematic. The third anion or an ancillary ligand associated with the rare-earth metal centers appears to play an important role in controlling the stereochemistry of the coordination sphere around the rare-earth metal centers. Using the same approach, we have also successfully isolated mono-metallic chiral 4f complexes of general formulae [Ln(Camph)4]-. The study of magnetic behaviors revealed Single Molecule Magnet (SMM) behavior for several complexes containing Tb or Dy ions
Shao, Feng. "Ingénierie de l’anisotropie magnétique dans les complexes mononucléaires de cobalt(II) et les métallacrowns à base de lanthanides". Thesis, Université Paris-Saclay (ComUE), 2017. http://www.theses.fr/2017SACLS126/document.
Testo completoAs we know, the applications are determined by properties, which are essentially determined by structure. The interplay between form (molecular structure) and function (physical properties) can be exploited engineering by the ligand, the metal ion, the metallacrown approach and so on. The work focuses on the synthesis and the study of the magnetic behavior of mononuclear cobalt(II) complexes with trigonal geometry and on the study of mononuclear lanthanide complexes that possess a metallacrown structure.For the cobalt(II) complexes, the aim was to tune the magnetic anisotropy by changing the nature of the tetradentate organic ligand and the terminal ligand. Almost all these complexes behave as Single Molecule Magnets with an energy barrier to the reversal of the magnetization that can be linked to their magnetic anisotropy and thus to the nature of the organic ligands. The lanthanide containing metallacrown complexes are highly symmetric, which allows performing a correlation between the nature of the lanthanide ion and their Single Molecule Magnet properties.The dissertation will be composed of 6 chapters. Chapter 1 introduces the background of the magnetism, Single Molecule Magnets, Single Ion Magnets, and some important SIMs. Chapter 2 focuses on a family of trigonal bipyramidal complexes [Co(Me6tren)X]Y. We show that the axial ligand affects the SMM behavior allowing us to prepare a complex with a magnetic bistability at T = 2 K. In Chapter 3, we examine the effect of changing the coordinated atoms (sulfur instead of nitrogen) in the equatorial coordination sphere of cobalt(II). We demonstrate that this slight change improves the SMM behavior. Chapter 4 and 5, which concern two series of 12-MC-4 SMMs based on LnGa4 (Ln = TbIII, DyIII, HoIII, ErIII, YbIII) with the ligands salicylhydroxamic acid (H3shi) and 3-hydroxy-2-naphthohydroxamic acid (H3nha), respectively, where we correlate the nature of the lanthanide ion to its magnetic behavior using ab initio calculations. At last, the understanding gained from this dissertation research, along with future research directions will be recapitulated in Chapter 6
Wang, Yiting. "Syntheses, Crystal Structures and Characterizations of Mono- and Polynuclear Ni- and Co-based Molecular Magnets". Thesis, Université Paris-Saclay (ComUE), 2019. http://www.theses.fr/2019SACLS225.
Testo completoThe objective of elaborating “magnets by design” can be achieved by tailoring the molecular structures of coordination complexes. The designed molecules are expected to exhibit the characteristics required for specific applications, virtually resulting from their rich structural diversity. Mononuclear Ni-based complexes with large magnetic anisotropy and polynuclear Ni- and Co-based molecules are designed in this dissertation. The syntheses, magnetic studies, and electrochemical properties of the complexes containing non-innocent bridge ligand are investigated. The Ni(II) mononuclear complexes with trigonal bipyramid geometry are prepared by tuning the axial ligands and the counter anions. The effect of the nature of the axial ligands and the structural change induces by the counter anions on magnetic anisotropy is studied experimentally and analyzed with the help of theoretical calculations. Large organic molecules are used to design trinuclear complexes with large magnetic anisotropy and weak exchange coupling. Several polynuclear Ni- and Co-based complexes with TTC³⁻ acting as an innocent bridging ligand and HHTP as a typical non-innocent ligand, are crystallized with various structures (TTC = Trithiocyanurate; HHTP = Hexahydroxytriphenylene). For the complexes containing the non-innocent ligand (HHTP), radical anions are produced by electrochemistry. The combination of spectroelectrochemical and Electron Paramagnetic Spectroscopy coupled to electrochemistry studies allow investigating the delocalization of the electrons on the generated organic radicals and the exchange coupling among the metal ions
Fernandez, Garcia Guglielmo. "Lanthanide-based SMMs : from molecular properties to surface grafting exploiting multi-level ab initio techniques". Thesis, Rennes 1, 2017. http://www.theses.fr/2017REN1S171/document.
Testo completoThe Ph.D. project was a joint agreement between two universities: Université de Rennes 1 in France and Università di Firenze in Italy. The project aimed to shed light on the rationalization of the inter- and intramolecular properties of novel lanthanide-based Single Molecule Magnets, SMMs, (“molecular part”) and their evolution once adsorbed on surface (“surface part”). Both aspects are examined within a theoretical and computational framework, with different multi-level techniques ranging from periodic Density Functional Theory (pDFT) to post-Hartree-Focks approaches, depending on the experimental observable of interest. SMMs are, indeed, at the cutting-edge in the design of novel magnetic materials in surface science (as spintronics or memory storage devices), but for their exploitation a deep understanding of their electronic and magnetic properties is needed
Bachschmidt, Anne. "Nouveaux matériaux photomagnétiques à base de polycyanométallates : des analogues du bleu de Prusse aux molécules à haut spin". Paris 6, 2007. http://www.theses.fr/2007PA066676.
Testo completoAdak, Abhijit. "Matériaux moléculaires magnétiques bidimentionnels construits à partir du ligand redox-actif pyrazine". Electronic Thesis or Diss., Bordeaux, 2023. http://www.theses.fr/2023BORD0479.
Testo completoThis thesis presents synthesis and characterizations of novel two-dimensional (2D) molecule-based magnetic materials based on redox-active pyrazine ligands and transition metals. The role of axial ligands in this kind of systems as well as post-synthetic technique to enhance the magnetic exchange interactions have been explored in this thesis. Chapter I discusses brief literature survey on molecule-based magnets and strategy to design high critical temperature (Tc) molecule-based magnets. Chapter II provides general concepts of magnetism, X-ray absorption spectroscopy (XAS) and X-ray magnetic circular dichroism (XMCD) that are essential for understanding of the experimental results obtained in this thesis. Chapter III describes synthesis and characterization of Cr(pyz)2I2 coordination solid and illustrates the role of post-synthetic modification in enhancement of magnetic ordering temperature (Tc). Chapter IV is devoted to investigate the role of axial ligand substitution in a family of coordination network V(pyz)2X2 (where, X = Cl, Br. I and NCS). Chapter V deals with the post-synthetic reduction of the coordination solids discussed in chapter IV
Chatelain, Lucile. "Conception d'assemblages polymétalliques d'uranium pour le développement de molécules aimants". Thesis, Université Grenoble Alpes (ComUE), 2016. http://www.theses.fr/2016GREAV076/document.
Testo completoThe study of actinide chemistry is not only essential for the development of nuclear fuel, nuclear fuel reprocessing or environmental clean up, but also for the understanding of fundamental actinide/ligand interactions and multiple bounding. The magnetic properties of polynuclear actinide molecules are of significant interest to investigate the magnetic communication between the metallic centres. Furthermore, they are highly promising for the design of molecular magnets. Uranium undergoes redox reactions due to a wide range of available oxidation states and easily forms polynuclear assemblies. However, only a few controlled synthetic routes towards these polynuclear uranium assemblies are described in the literature. In this context, the first part of this work was dedicated to the synthesis of oxo/hydroxo uranium clusters from the controlled hydrolysis of tetravalent uranium in the presence of an environmentally relevant ligand. This led to the synthesis of clusters with novel topologies, for which size could be varied as a function of the reaction conditions employed. However, the obtained clusters do not behave as SMM. In order to gain a stronger interaction between metallic centres, the cation-cation interaction was used to rationally design polynuclear uranyl(V) complexes. The isolation of uranyl(V) complexes had been limited in the past by its disproportionation, however, a fine tuning of the organic ligand and reaction conditions finally allowed to stabilise uranyl(V). We used stable uranyl(V) units as building block to form heteronuclear complexes with 3d and 4f metals with polymeric or discrete structures. The study of the magnetic properties of the uranium polynuclear assemblies was carried out and revealed single molecule or chain magnet behaviours with high energy barriers. The uranyl(V) unit was also used as a structural model for the more radioactive neptunium element, allowing the isolation of an isostructural trinuclear neptunyl(V) assembly in similar reaction conditions. Finally, the use of a nitride ligand as a bridging unit, allowing the formation of uranium-ligand multiple bonds, was explored to build novel di-uranium complexes supported by siloxy ligands. Nitride molecules containing unprecedented uranium in the +III oxidation state were isolated and characterised
Kerkache, Asma. "Nouveaux chemins d'accès à des molécules-aimants multifonctionnelles par post-fonctionnalisation". Thesis, Lyon, 2021. http://www.theses.fr/2021LYSE1307.
Testo completoVirtual storage spaces (Cloud) has become common today. However, these are not dematerialized and are hosted in data centers (Data Center), they are bulky and energy consuming. Research in the field of magnetic information storage has made considerable progress with, among others, the discovery of single-molecule magnets (SMMs). These compounds could significantly increase the storage capacities of future hard drives. Magnet molecules are complexes of coordination chemistry or organometallic chemistry, isolated from each other. They have intrinsic magnetic properties unlike conventional magnets where the magnetic information retention properties come from a cooperative effect of all molecules in the material. This therefore results in a noticeable difference in the capacity for storing information. The first magnet-molecule, the famous [Mn12], was discovered in 1980. Its magnetic properties were characterized a few years later, thus opening a new chapter in the field of molecular magnetism. The characteristics of a molecule-magnet are linked to the energy barrier that defines these complexes: ΔE = | D | S² (D for anisotropy and S for the spin of the complex). From 2003, the replacement of transition metals by lanthanide ions revolutionized research in this field. Previous laboratory work has shown that the nuclearity of molecular structures and the number of ligands have a major impact on the magnetic properties of the molecule-magnet. It turns out that the simplest complexes are generally those with the best performance. The main subject of the thesis is to develop mononuclear complexes. The idea is to be able to subsequently modify these compounds by post-functionalization of the organic ligand in order to exacerbate the magnetic performances and / or to add new properties (luminescence for example, multifunctionality) to the initial molecule-magnet. To do this, a library of original β-diketone ligands was produced. These ligands have functions which subsequently make it possible to carry out organic modification reactions on the magnet molecule. Two post-functionalization reactions were thus considered: a Palladium-coupling reaction (Sonogashira or Suzuki-Miyaura) and a click reaction (Huisgen cycloaddition). A second aim of this thesis is based on the results of a recent theoretical study which proposes the use of the sulfur atom in the coordination sphere of the metal center of the SMM. The latter would improve the axiality of the molecule and therefore the magnetic properties of the final molecular structure. The synthesis of sulfur analogues of β-diketone ligands was then undertaken to study the influence of the sulfur atom compared to its oxygenated counterparts in the final magnet molecule. β-monothioketone and keto-sulfoxide ligands have therefore been synthesized. The corresponding lanthanide ion-based complexes have been isolated, their molecular structures as well as their magnetic and luminescence properties have been characterized
Atzori, Matteo. "Anilate-based Functional Molecular Materials with Conducting and Magnetic Properties". Thesis, Angers, 2015. http://www.theses.fr/2015ANGE0009/document.
Testo completoThis work explores the potential of anilate-based ligands in the synthesis of new rational designed functional molecular materials exhibiting improved magnetic and conducting properties. Anilates, namely 3,6-disubstitued 2,5-dihyroxy-1,4- benzoquinones in their dianionic form, have been selected as ligands since their electronic/structural features, coordination modes and ability to mediate magnetic exchange interactions between coordinated metal centers make them potential candidates for the preparation of theabove-mentioned materials. Various anilate derivatives have been used for the preparation of a family of rationally designed tris-chelated octahedral paramagnetic metal complexes of general formula [MIII(X2An)3]3- (MIII = Cr, Fe; X = Cl, Br, I, H, Cl/CN, An = C6O4 2- = anilate). These paramagnetic metal complexes have been thoroughly characterized and used, in turn, as molecular building blocks for the preparation of i) a family of molecule-based magnets, where subtle changes in the nature of the substituents on the anilate moiety were employed as “adjusting screws” in tuning the magnitude of the magnetic interaction between the metals, and thus, the magnetic properties, ii) hybrid paramagnetic molecular conductors in combination with the BEDT-TTF organic donor, iii) a complete series of isostructural chiral molecular conductors obtained by combining the TMBEDT- TTF chiral donor with 2D heterobimetallic anionic layers obtained in situ by the self-assembling of tris (chloranilato)ferrate(III) metal complexes and potassium cations.Moreover, novel anilate derivatives showing electroactive and luminescent properties have been further synthesized, highlighting the versatility of the anilate moiety to be functionalized with suitable substituents carrying selected physical properties
Bulicanu, Vladimir. "Synthesis and study of magnetic molecular materials based on Co(II) and Cr(II) trinuclear clusters containing M-M bonds". Thesis, Bordeaux, 2016. http://www.theses.fr/2016BORD0239.
Testo completoIn this thesis is described the synthesis, structures and magnetic properties of coordination compounds containing Co-Co or Cr-Cr bonds. In the first part of this work a general background is given on the historical evolution of this type of coordination chemistry. In the second chapter the possibility of incorporating a {Co3} cluster with dipyridylamide ligands and intermetallic bonds into one-dimentional coordination polymers is discussed. The interactions between spin centers and the effect of the bridging ligand were studied, and changes in the spin crossover properties were monitored and compared to the precursor. In the third chapter the Single-Molecule Magnet properties of a series of {Cr3} clusters are presented. The influence of the axial ligand and the symmetry of the molecule was considered and correlated to the magnetic properties. In the fourth chapter the phenomenon of coordination induced spin transition in a {Co3} cluster with dipyridylformamidinate ligands is discussed. Changes in magnetism and optical properties as a result of the breaking and restoring of a Co-Co bond were monitored as a function of temperature and light irradiation
Bez, Riadh. "Nouveaux aimants nanocomposites à base d'intermetallique de terre rare". Thesis, Paris Est, 2015. http://www.theses.fr/2015PESC1162.
Testo completoThis work focuses on the synthesis and the study of new hard / soft nanocomposites. These nanocomposites exhibit interesting magnetic properties thanks to their high remanence combined with a high coercivity Hc. This allows a huge increase of the specific energy of the magnet. In this context, we have developed and studied new nanocomposites based on the out of equilibrium hard phases Sm (Fe, Si) 9C and Sm (Fe, Ga) 9C and soft phases _-Fe and FeCo. For the intrinsic nanocomposites SmFeSiC /_-Fe, we have shown by transmission electron microscopy, an average grain size of about 20 nm for the studied samples. The maximum value of (BH) max is obtained for the nanocomposite with about 15 % of _-Fe, it is equal to 11.7 MGOe (93.6 kJ/m3). For the extrinsic nanocomposites SmFeSiC/FeCo et SmFeGaC/FeCo, we have shown that the energy product (BH) max reaches a maximum and then decreases with increasing the rate of FeCo. The maximum values obtained are about 13.5 MGOe (108 kJ/m3) and 12.4 MGOe (99.2 kJ/m3) for SmFeGaC / 20% FeCo and SmFeSiC/ 10% FeCo samples, respectively. Finally, we have investigated the local structure of Pr2 (Co,Fe) 7 alloys by EXAFS spectroscopy and we have shown that the preferential site Fe in these compounds is the 12k site
Grumbach, Nathan. "Auto-organisation de molécules-aimants et de nanoparticules magnétiques sur des surfaces de copolymères dibloc". Strasbourg, 2009. http://www.theses.fr/2009STRA6259.
Testo completoMagnetic information storage, used in hard disks notably, has not stopped evolving toward higher storage density. Current storage systems reach their physical and technological limits, and future improvements will necessarily consist in new materials and technologies. We have studied in this work two kinds of new magnetic nanometric objects, Single Molecule Magnets (SMM) and magnetic nanoparticles, both showing magnetic bistability at the isolated individual object. These materials could help overpass current limitations and make magnetic storage densities increase by up to five orders of magnitude. This work is focused on the multiscale organisation of these objects on a surface, with the aim of forming two dimensional organised networks. The nano-objects we considered can self-organize on a surface, but correlation lengths remain short. To control and propagate nanometric organisation up to macroscopic scales, we functionalize the surface using PS-PMMA block copolymer and use microphase separation in order to structure the surface in ten nanometers wide stripes. Oriented demixtion of the block copolymer is obtained via templated self-assembly, in our case by using a surface patterned with 100 to 200 nm wide channels. Then the magnetic nano-objects selectively self-organize in networks on the polymer stripes. Multiscale spatial organisation of nanometric objects is therefore possible by combining top-down lithographic and bottom-up self techniques. Experimental study of magnetic properties of organised monolayers of SMM is challenging and has been performed with Low Temperature XMCD. We have shown that Mn12-like SMMs remain structurally intact at the surface but that their magnetic properties are unfortunately lost. Still, other SMMs or magnetic gold nanoparticles remain interesting candidates for high density magnetic storage. Finally, we have shown that the organised deposition of these nano-objects can result in magnetic anisotropy, with a large range of potential applications
Bretosh, Kateryna. "Edifices supramoléculaires fonctionnels : vers des aimants performants". Thesis, Toulouse 3, 2019. http://www.theses.fr/2019TOU30287.
Testo completoThis thesis deals with the control of magnetic anisotropy in the design of molecule-based magnetic materials. Magnetic anisotropy is highly related to the coordination environment of a metal ion. Herein we focused on 3d metal ions with pentagonal bipyramid coordination spheres that may exhibit a rather large magnetic anisotropy. A series of seven coordinate Fe(II) and Ni(II) complexes formed with a neutral pentadentate cyclic ligand (LN5PhenMe) were synthesized and their magnetic behaviors investigated. They have been found to exhibit axial (Ising-type) magnetic anisotropy with a negative zero-field splitting axial parameter D. Modulation of magnetic anisotropy was studied for Fe(II) complexes with various substituents in axial position (Fe(II)LN5PhenMeX2, where X= Cl-, Br- , I-, NCS-, ROH, {Ni(CN)4}2-) revealing D values spanning from ca -4 to -17 cm-1. Due to the large axial anisotropy induced by heavier halogen atoms in Br and I derivatives, these complexes showed SMM (Single Molecular Magnet) properties with energy barrier Ueff/kB ~ 70 K. These complexes are structurally robust and can be used as building units to form polynuclear systems. Their combination with a related trans-cyano K[CrLN3O2Ph(CN)2] complex allowed the synthesis of trinuclear complexes [{CrLN3O2Ph(CN)2}2MLN5PhenMe] (M= Fe(II) or Ni(II)), and a 1-D coordination polymer [{CrLN3O2Ph(CN)2}MLN5PhenMe][ClO4]n showing respectively, SMM and SCM (Single Chain Magnets) behaviors. The latter is the first example of SCM made with pentagonal bipyramid Ni centers
Bridonneau, Nathalie. "Architectures multimétalliques fonctionnelles : comportement de molécule-aimant et photo-magnétisme". Paris 6, 2013. http://www.theses.fr/2013PA066570.
Testo completoThis work focuses on the synthesis of discrete molecules showing bifunctionality based on single-molecule magnet behavior or photo-switchable processes. The first part of this work concerns information storage at the molecular scale via the synthesis of anisotropic high spin compounds displaying a single-molecule magnet behavior. New compounds (CoMn6, CrMn6, S = 21/2) have been obtained showing the important role of the control of intermolecular interactions. Particular attention has been paid to the design of multifunctional supramolecular architectures bearing three or four different metal ions. Using the strategy « polynuclear complexes as ligand », new families of compounds have been developed, exhibiting different topologies such as derivatives of CoTbCu complexes or hetero-tetra-metallic compounds (i. E. MoCuTb-Ni). The second part of this work is devoted to the synthesis of photomagnetic « Molybdenum-Copper » complexes. The synthesis of model compounds, MoZn2 and MoZn0. 95Cu0. 05, and the study of the photo-induced metastable states enabled a better understanding of the photomagnetic behavior. Thus, a spin transition on the molybdenum center and a photo-induced electron transfer from the molybdenum to the copper has been demonstrated. Higher nuclearity compounds have also been obtained, Mo3Cu4 and Mo6Cu13. Finally, the deposition of photo-magnetic molecules on surface as also been carried out using Langmuir-Blodgett technique
Archet, Florence. "Cellules solaires organiques à base de molécules bio-inspirées". Thesis, Bordeaux, 2018. http://www.theses.fr/2018BORD0400/document.
Testo completoTo face the growing needs in energy, renewable energies like solar photovoltaic represent realistic solutions. Photovoltaic energy requires efficient materials to absorb photons and to convert them into electricity. Organic solar cells (OSCs) are based on semiconducting π-conjugated polymer or small molecules. Current research in this field focuses on three main topics: the reduction of costs, the increase of device lifetime and the increase of power conversion efficiency. This last issue led to an increase in the complexity of OSCs architecture as well as organic semi-conductors, leading to anincrease in manufacturing costs. In order to develop sustainable and eco-friendly processes, it is now important to work on cost effective semi-conductors obtained fromgreen synthetic methodology. The aim of this thesis was to develop new bio-inspired organic semi-conductors. These materials are potentially low cost. Molecules studied present donor-acceptor-donor structure. They have the skeleton of curcumine. Curcumine is a natural yellow dye present in curcuma. Acceptor group is boron difluoride. Donor groups vary depending on the curcuminoid derivative. Optoelectronicproperties of seventeen semi-conductors were studied. Several of them stood out: those with anthracene groups, those with thiophene derivatives, finally and especially, those with triphenylamine groups. For this last family, the impact on the photovoltaic performances of the ink formulation used for deposition has been deeply studied. Several acceptor materials were tested, as well as ternary blend. For one curcuminoid derivative combined with PC61BM, efficiency above 4% has been achieved with open circuit voltage up to 1.0 V. Due to the very simple chemical structure of the donor, this represents one of the best result reported in literature to our knowledge. Transient species were also studied by ultrafast spectroscopy. The fabrication process was also changed to eliminate halogenated solvent and to enable processing in ambient air like in industrial process. Finally, photovoltaic properties observed are interesting. Nevertheless, they are not sufficient for industrial application due to low hole mobility in these materials
Jeon, Ie-Rang. "Organisation par chimie de coordination de molécules-aimants : vers une nouvelle génération de matériaux magnétiques et photomagnétiques". Thesis, Bordeaux 1, 2012. http://www.theses.fr/2012BOR14614/document.
Testo completoThe beginning of the 1990’s marked the discovery of Single-Molecule Magnets (SMMs), which created the hope tostore information on a single molecule due to their magnetic bistability. However, it is becoming of strategicimportance to dedicate a part of our research to their organization in order to achieve devices for the potentialapplication. During this thesis work, our strategy was to exploit coordination chemistry to organize these moleculesin a controlled way by using different types of linkers.Chapter I covers theoretical backgrounds for this research project. In this chapter, Single-Molecule Magnets(SMMs), Single-Chain Magnets (SCMs), Spin Crossover (SC) and Electron Transfer (ET) systems are described anddiscussed. Chapter II contains relevant literature on SMM-based coordination networks and photoactive cyanidobasedbimetallic systems. Chapter III presents the organization of [Mn4] SMMs in 1D and 2D networks withdiamagnetic linkers (chlorido ions) or paramagnetic linkers containing NiII, MnII, and CuII ions. The extensivephysical studies (X-ray crystallography, magnetic and heat capacity measurements, and theoretical analysis) on thesenetworks demonstrated new magnetic behavior and enhanced energy barrier compared to the isolated [Mn4] SMMs.In Chapter IV, we prepared new switchable linkers based on the cyanido-bridged Fe/Co unit, to realizephotomagnetic networks of SMMs. A rational building-block approach has been used to design these dinuclearFe/Co complexes. Extensive spectroscopic, electrochemical and magnetic characterizations have been performed tounambiguously reveal in one of the synthesized complexes the presence of a spin crossover induced by temperaturein the solid-state, and an intramolecular electron transfer assisted by controlled protonation in solution, bothaccompanied by optical and magnetic changes. For the first time, this new complex shows two distinct switchingprocesses depending on its physical state and external stimuli
Huang, Gang. "Synthesis, crystallographic and magnetic studies of lanthanide-based molecular edifices". Thesis, Rennes, INSA, 2017. http://www.theses.fr/2017ISAR0008/document.
Testo completoSingle-molecule-magnet (SMM) has attracted increasing attention in recent years due to their appealing potential for high-density storage devices. Much effort has been made to improve the magnetic performance through flexible coordination chemistry strategy.In this thesis, the work is organized in two main parts. The first part is constituted of chapter 2 and chapter 3, primarily focus on the Ln-Radical families aiming at designing zero-dimensional and one-dimensional single-molecule-magnet (SMM). The second part contains chapter 4 and chapter 5, in which the ligands are replaced by diamagnetic ones for the purpose of designing the multifunctional materials.In the first part, nine TEMPO-R (R represents the substituent) radicals are employed to construct zero-dimensional and one-dimensional complexes. These kinds of compounds were prepared by reactions in the dichloromethane/n-heptane co-solvents between the precursor [Ln(hfac)3(H2O)2] and TEMPO radicals. Subsequently their molecular structure as well as magnetic properties have been characterized and described. In chapter 2, four radicals (TEMPO-OCH3, TEMPO-NH2 TEMPO-Acetamido and TEMPO-OCH2CCH) are used to synthesize monometallic or dimetallic complexes, among which three are successful to construct the SMM. For the special case of TEMPO-OCH3 a rare light lanthanide ions (CeIII, PrIII and NdIII) SMM behavior is reported. The PrIII derivative is the first PrIII-based SMM ever reported. In chapter 3, the target is to design SMM in one dimension by using another five radicals: TEMPO-Methacrylate, TEMPO-OCOPh, TEMPO-oxo, TEMPO-OH and TEMPO-CN. Among all the chains, [Pr(hfac)3(H2O)(TEMPO-OH)]n (17), [Dy(hfac)3-TEMPO-OH)]n (18) and [Tb(hfac)3(TEMPO-CN)]n (22) are identified as chains of SMM. 22 exhibits the slowest magnetic relaxation among all the 4f-2p SMMs obtained in this thesis, with a small opening of magnetic hysteresis. Its analogue of [Gd(hfac)3(TEMPO-CN)]n (23) even exhibits one of the largest exchange values in Gd-2p compounds. Last a very rare example of bidimensional 4f-2p network of formula [(Ce(hfac)3)3(Oxo-TEMPO)4]n (15) is obtained.In chapter 4, the salt of a photo-switchable carboxylic ligand was reacted with LnIII ions to afford a chain-like arrangement of dinuclear complexes of formula [Ln(AZO)3(DMSO)(H2O)]2•4DMSO. Photo-sensitivity of the ligand under the irradiation of UV has been tested together with magnetic measurements in solution. In chapter 5, a Metal-Organic-Framework (MOF) (28) has been designed and characterized. Ln-Ln ferromagnetic interaction has been observed and diamagnetic doping highlight that, contrary to what observed on [Ln(AZO)3(DMSO)(H2O)]2•4DMSO, this interaction promote SMM behavior in a so-called MOF-SMM
Dupont, Louis. "Développement d'un dispositif de champ magnétique réversible à base des cryo-aimants supraconducteurs". Thesis, Normandie, 2018. http://www.theses.fr/2018NORMC209/document.
Testo completoSuperconducting cryomagnets are high magnetic fields sources that are both compact and energy efficient. There are various magnetization technics but only the magnetization by pulsed magnetic field (PFM) results in high excitation fields, that otherwise could only be obtained with large superconducting coils.This work was done in the framework of an industrial collaboration. In a first step, a compact and innovative pulse current generator enabling the generation of pulses with a 3000 Amps maximum intensity was designed and fabricated. Secondly, different systems for the magnetization of cryo-magnets either cooled down to 77 K or cooled in a cryostat by a cryo-generator were implemented. Finally, the pulsed field magnetization of superconducting cryo-magnets has shown that reversible and reproducible magnetic field in the one Tesla range could be generated by the set up.The results obtained are consistent with the industrial goals of this study. They are very encouraging for the development of reversible magnetic field devices based on superconducting cryo-magnets and dedicated to scientific instrumentation or for electrotechnical applications
Hu, Lei. "Molécules conjugées en étoile à base d'azophénine : synthèse et caractérisation photophysique". Thèse, Université de Sherbrooke, 2017. http://hdl.handle.net/11143/11410.
Testo completoAbstract: This thesis presents the design, synthesis and photophysical investigation of various azophenine derivatives as “one unit” structural models for emeraldine, a mixed-valence form of polyaniline. Azophenine is a star-shaped cross-conjugated molecule containing both quinone diimine and phenyl amine residues included in emeraldine but both, azophenine and emeraldine, are reported notoriously non-emissive. The challenge was to render azophenine emissive at room temperature prior any photophysical investigation. The long-term objective is to render polyaniline, in one form or the other, useful in bulk heterojunction solar cell in the active layer as it is not expensive. Because of solubility issues, the use of models becomes very appealing. The considered structural modifications include the anchoring of ethynyl-bridged functions at the para-position of the four phenyl groups of azophenine. These functions are the bulky truxene aromatic, the organometallic trans-bis(trialkylphosphine)platinum(II) pendent groups, and zinc(II)porphyrin and BODIPY dyes. All these functions exhibit fluorescence or phosphorescence, signal that can be used to monitor any electronic interaction between these pendent groups and the central core. Their photophysical properties were investigated in detail using steady-state and ultrafast time-resolved UV-vis absorption and emission spectroscopy. DFT and TDDFT were also employed for geometry optimizations (DFT) and nature and positions of the CT absorption (TDDFT). Chapter 2 introduces the synthesis and characterization of a truxene-based star-shaped azophenine derivative called TertTruQ. The coupling of bulky truxene residues with azophenine improved the photophysical activity of the lowest energy singlet excited state (i.e. CT state) of this derivative at 77 K. Speculations are that the rate for non-radiative deactivation, namely internal conversion, decreased upon slowing down the rotations around the N-C bonds due to the size of truxene. Moreover, this new substituted azophenine turned out to be fluorescent in the solid state at room temperature. Because of these interesting new observations, the emission properties of emeraldine base form were re-examined. A weak fluorescence at ~780 nm at 77 K, confirmed by the excitation spectrum, demonstrated the presence a CT near-IR fluorescence for TertTruQ. Thus, azophenine provides a useful model to identify what simple structural modification that can be performed to render emeraline emissive, if possible at room temperature. Again, when a non-luminescent species becomes emissive, this change is accompanied by an increase of its excited state lifetime. Longer excited state lifetimes are more prone to solar cell applications. This work has been published in Physical Chemistry Chemical Physics, 2017. Chapter 3 describes the synthesis and characterization of trans-bis(trialkylphosphine)diethynyl-platinum(II)-containing azophenines forming the di- and tetra-substituted derivatives DiTruPtQ and TertTruPtQ. Both complexes exhibit fluorescence and phosphorescence of the organometallic “arms” at 298 K in fluid solution. Moreover, the heavy atom effect of platinum gave the possibility of exploring the triplet state properties of azophenine. However, the sought phosphorescence from the triplet CT state was not seen most presumably due to the fast non-radiative processes. This work has been published in Organometallics, 2017, 36(3), 572-581. Chapter 4 presents the effect of the replacement of the labile H+ ions on the HN^N moiety by BF2+ fragments to form cycles thus providing a more rigid framework for azophenine. Indeed, the CT near-IR fluorescence was observed both at 298 and 77 K. However, despite the presence of Pt in the pendent groups, no phosphorescence was detected. DFT computations suggested that the low-lying triplet state was very low (0.975 (BQ) and 0.84 eV) inducing a higher probability of non-radiative processes thus efficiently depleting the triplet state. This work has been submitted to Inorganice Chemistry. Chapter 5 introduces the well-known BODIPY and zinc(II)porphyrin fluorescent dyes, which were linked to azophenine to form DiBodipyQ, TertBodipyQ and PorBodipyQ. The absorption spectrum of Bodipy lies in a range where porphyrin does not absorb very much. So, the combination of these two chromophores along with the formation of a low-lying CT band improves the light collection of the solar radiation. Consequently, it was important to verify that the collected energy could easily transferred from one chromophore to another. Indeed, the 1Bodipy* → 1zinc(II)porphyrin and 1Bodipy* → 1CT(azophenine) were observed along with an efficient deactivation from 1zinc(II)porphyrin ~~> 1CT(azophenine).
Doungmene, Floriant. "Molécules et matériaux à base de polyoxométallates pour l’énergie et l’environnement". Thesis, Paris 11, 2014. http://www.theses.fr/2014PA112173/document.
Testo completoThe present work concerns the synthesis and characterisation of new polyoxometalate (POMs) based molecules and materials for applications in energy and environment matters. As far as the environment is concerned, our efforts involved the electro-catalytic and photo-catalytic transformation of pollutants such as nitrogen oxides and recalcitrant azo dyes like Acid Orange 7. As for the domain of energy, we focused on electro-catalytic systems aimed at producing dihydrogen (a high calorific power fuel) and at reducing dioxygen (an important reagent in fuel cells). These reactions usually require several electrons in order to take place, which led us to choose POM-based catalysts. In fact, POMs are capable of stocking and returning an important number of electrons without changing their structure.In the first part, several POMs in which different transition metals are sandwiched in the equatorial plane of the molecular scaffold are synthesised and characterised by experimental (cyclic voltammetry, coulometry, microbalance) et theoretical (DFT calculations) methods. These compounds have shown a very good electro-catalytic activity towards the reduction of substrates such as nitrogen oxides, dioxygen and hydrogen peroxide.In the second part, some materials exhibiting improved properties are synthesised through the incorporation of POMs in matrices like Metal Organic Framework (MOF)-type molecular networks and ionic liquid polymers. The association with a semi-conductor such as TiO₂ has also been considered. The materials obtained were characterised by several techniques: Fourier transform infrared spectroscopy, electrochemistry, diffuse reflectance spectroscopy, thermogravimetric analysis, X ray diffraction, X ray photoelectron spectroscopy, transmission electron microscopy. The POM and MOFs based materials are very performing for the electro-catalytic reduction of protons, having onset potentials better than those exhibited by platinum electrodes. The hybrids consisting of POMs, ionic liquid polymers and TiO₂ are photo-sensitive under visible light, unlike each component taken individually. They have shown a good activity towards the degradation of Acid Orange 7. In addition, the composite obtained by photo-deposition of silver nanoparticles on these materials exhibits a good electro-catalytic performance as a cathode for the reduction of O₂ and NO‾₃
Cosquer, Goulven. "Magnétisme et luminescence de complexes d'ions 3d , 4f et 3d4f à ligands électroactifs tétrathiofulvalène : vers des matériaux à propriétés multiples". Rennes 1, 2012. http://www.theses.fr/2012REN1S129.
Testo completoMulti-functional molecular materials have a high interest for their physical properties, and their small size. This work has allowed the synthesis of 5 ligands based on the TTF fragment, and the obtaining of five families of 3d, 4f, and 3d4f ion complexes. The crystallographic structures of these five families were obtained. The luminescence of two families of 4f complexes was measured highlighting the enhancement of the luminescence intensity and the increase of the excited state lifetime when the ligand is alkylated. A quantitative analysis of the magnetic properties of 4f and3d4f complexes was developed and permit to determine the splitting of the MJ energy levels of the ground state of the lanthanide ion, and the intensity of magnetic exchange interaction between the copper and lanthanide. This calculated splitting has been correlated with the splitting obtained through the luminescence spectrum in the case of the ion ytterbium. Both dysprosium complexes display single molecule magnet behaviour. The role played by the presence of hydrogen bonding could be revealed by susceptibility measurements in solution, and by the alkylation of the ligand. The increase of the energy barrier value was correlated with the increase of the coordination polyhedron symmetry around the lanthanide ion
Cahier, Benjamin. "Étude théorique de l'anisotropie magnétique dans des complexes de métaux de transition : application à des complexes mono- et binucléaires de Ni(II) et Co(II)". Thesis, Université Paris-Saclay (ComUE), 2018. http://www.theses.fr/2018SACLS070/document.
Testo completoSingle molecule magnets are molecular complexes containing transition metal or lanthanides ions which are able to block their magnetization below a certain blocking temperature Tb. This blocking is caused by an energy barrier separating the two orientations of magnetization leading to two stable magnetization states. These two states can be controlled by an external magnetic field.Therefore, it is theoretically possible to use these molecules as bits which are able to store“classical” information. However, due to the quantum nature of these molecules, the relaxation of magnetization can exist even at low temperatures. This phenomenon is called the quantum tunneling effect and prevents the bistable (classical) behavior of the magnetic properties, as well as their use as classical bits for data strorage.Yet, the quantum tunneling of the magnetization also leads to a particular situation at a low temperature where two levels are separated by an energy related to the non-axial character(rhombic) of the magnetization (when the spinis an integer). Such two-levels system could be used as a quantum bit (qbit) which is the basic unit for quantum information processing. Thus,the design of classical or quantum bits require a precise understanding of magnetic properties and their origin at a microscopic level.The Ph.D work was devoted to the theoretical study of the magnetic anisotropy in mononuclear and binuclear Ni(II) (S=1) and Co(II) (S=3/2) complexes. Ab initio calculations based on the wave function theory were carried out and the spin Hamiltonian parameters were extracted. Model complexes were used to investigate the structural and electronic parameters causing magnetic anisotropy.Calculations were, also, performed on complexes synthesized in the laboratory.Comparison between real and model complexes allowed rationalizing the magnetic properties and imagining new synthesis strategies leading to the desired magnetic properties. Binuclear complexes that can be considered as double qbits and used to build quantum logic gates were also investigated. The calculations were performed by fragmenting the binuclear complexes into two mononuclear units in order to study the local anisotropy of each metal ion.The exchange interaction was investigated using Density Functional theory (DFT). In order to study the influence of an external perturbation on magnetic properties, the magnetic properties of a mononuclear Co(II) complex under an external electric field applied parallel or perpendicular to the axis of easy magnetization were calculated. The application of an electric field can lead to important modifications of magnetic properties. Thereby, offering the possibility to the manipulation of these molecules by external electric fields
Maury, Claire. "Genèse de la microstructure des aimants permanents de type 2:17 à base (Sm,Co)". Grenoble INPG, 1992. http://www.theses.fr/1992INPG0032.
Testo completoFeng, Min. "Multiple physical properties in the lanthanide complexes involving 2,6-di(pyrazol-1-yl)- pyridine-based tetrathiafulvalene ligands". Thesis, Rennes 1, 2015. http://www.theses.fr/2015REN1S113.
Testo completoIn this manuscript, the Chapter one introduces the target multifunctional materials, including the necessary knowledge of different selected physical properties such as magnetism, luminescence, and conductivity, as well as some of the previous contributions by our and other groups. In Chapter two, the tetrathiafulvalene-based ligand with two dpp acceptors (L1 and L2) (TTF = tetrathiafulvalene, dpp = 2,6-di(pyrazol-1-yl)-pyridine) and the corresponding lanthanide complexes are presented including the synthesis and physical characterizations: single crystal structure, cyclic voltammetry, absorption spectra that rationalized by TD-DFT calculations, emission spectra, and DC and AC magnetic measurements. The complexes Eu, Yb, and Er are emissive. In the Chapter three, a TTF-based ligand with two hetero coordinating sites L7 and its two Dy(III) complexes (C7-1 and C7-2) were presented, which show multi-relaxation SMM behavior
Tyrman, Muriel. "Vers une alternative aux aimants à base de terres rares : hexaferrites nanostructurés et alliages Mn-Al". Thesis, Université Paris-Saclay (ComUE), 2017. http://www.theses.fr/2017SACLV022.
Testo completoIn the context of green car development for mass market, development of low cost rare-earth-free magnets is clearly a milestone, because the rare-earth are expensive and their production is not ecological and a monopoly of one country. Two routes are explored herein : nanostructuration of M-type hexaferrites by flash sintering (Spark Plasma Sintering), and the synthesis of Mn-Al-C alloys by melt spinning. Concerning the first material, the optimization of the synthesis protocol allowed to increase the coercive field by a factor of 2. Two characterization tools of the magnets were set-up : the first evaluates the texture of the material (Stoner and Wohlfarth model), the second, based on Preisach model, is used to infer the magnetization processes. For Mn-Al-C alloys, we have evidenced from Weiss plots the antiferromagnetic coupling between 1a and 1d-sites Mn atoms. Neutron diffraction confirmed this result and shown that the magnetic moment of the 1d-site Mn is also much larger than that of 1a-site. Cryogenic ball milling followed by high-pressure SPS (400 MPa) increased the coercive field by 40 %. The results obtained are very promising as to the feasibility of alternatives to rare-earth magnets
Cotelle, Yoann. "Clips moléculaires à base de tétrathiafulvalène : Synthèse et reconnaissance de molécules neutres électrodéficientes". Thesis, Angers, 2014. http://www.theses.fr/2014ANGE0011/document.
Testo completoNo english summary
Braiek, Mohamed. "Développement des biocapteurs à base de molécules auto-assemblées et de polymères nanostructurés". Thesis, Lyon 1, 2013. http://www.theses.fr/2013LYO10070.
Testo completoPianet, Vivien-Maxime. "Propriétés statiques et dynamiques des chaînes aimants". Thesis, Bordeaux, 2014. http://www.theses.fr/2014BORD0245/document.
Testo completoThe size reduction of magnetic units able to store information is an important issue for the design of high-density data storage devices. The discovery of molecules that show slow relaxation of their magnetization, similar to classical magnets, is a great breakthrough in terms of molecular scale information storage. The work presented in this thesis is devoted to the study of the magnetic properties of Single Chain Magnets. Single Chain Magnets can be viewed as a one-dimensional assembly of anisotropic magnetic units linked by magnetic interactions. Beyond their potential applications, Single Chain Magnets are interesting prototypes for the fundamental study of spin chains. The first chapter of this manuscript summarizes some known static and dynamic properties of Single Chain Magnets. Chapter II is devoted to the static properties of domain walls, which link the magnetic domains in spin chains, considering various magnetic topologies. Chapter III is dedicated to the dynamic properties of Ising spin chains. In the Single Chain Magnet literature, the Glauber model is used to describe the dynamic properties of such spin chains. However, there exists an infinite number of dynamic Ising models. In this chapter, three dynamic models are studied in detail. We show that the presence of a magnetic field allows us to discern different magnetization relaxation behaviors associated with each dynamic model. These results allow us to establish two experimental protocols in order to determine the most suitable dynamic model to describe the properties of Single Chain Magnets
Derkaoui, Souad. "Effet de Cu et Zr sur les caractéristiques métallurgiques et magnétiques des alliages à base de SmCo5 et Sm2Co17 pour aimants permanents". Grenoble INPG, 1987. http://www.theses.fr/1987INPG0061.
Testo completoHosseini, Tehrani Atoosa. "Etude et réalisation de photorécepteurs pour les longueurs d'onde 1,3 um - 1,55 um intégrés monolithiquement à base de nouvelles structures semiconductrices à fort désaccord de mailles". Lille 1, 1989. http://www.theses.fr/1989LIL10029.
Testo completoMoreau, Mathieu. "Marquage de molécules biologiques par des complexes de radiométaux à base de polyamines macrocycliques". Phd thesis, Université de Bourgogne, 2012. http://tel.archives-ouvertes.fr/tel-00796881.
Testo completoBabé, Céline. "Oxydes simples et mixtes à base de ZnO pour l'adsorption réactive de molécules organosoufrées". Lyon 1, 2008. http://www.theses.fr/2008LYO10167.
Testo completoRecent legislation impose that in 2009 sulfur content in gasoline and diesel to be less than 10 ppm. Today hydrodesulphurization allows to get this value but it is expensive, and new processes are therefore developed. Among these alternative processes, the reactive adsorption which allows removing sulfur keeping the hydrocarbon chain in the feed appears promising. The aim of our work is to study zinc, iron and aluminum based oxides on which can be used in such a process. To understand the effect of each element (Zn, Fe and Al), simples, doubles and triples oxides have been examined. The study of ZnO sulfidation by H2S allows us to perfect a method on the use of breakthrough curve. A geometric and kinetic modeling of the sulfidation demonstrates that large particles are not completely sulfided due to a diffusion limitation in ZnS. Studies of the sulfidation of oxides by H2S and of the reactive adsorption of DBT (model molecule of refractory compound in diesel) show that simple oxides (ZnO, Fe2O3) are completely sulfided with H2S but don’t react with DBT. To perform reactive adsorption of DBT, the solid must contain iron for the desulphurization of the molecule and zinc to adsorb sulfur
Dang, Minh Trung. "Elaboration de cellules solaires photovoltaïques à base de polymères conjugués : études des systèmes réticulables". Thesis, Bordeaux 1, 2009. http://www.theses.fr/2009BOR13892/document.
Testo completoThis contribution deals with the elaboration of polymer-based photovoltaic solar cells. At first, this work was devoted to validate the experimental procedure in our laboratory. We fabricated cells consisting of the conjugated polymer poly (3-hexylthiophene) (P3HT, electron donor) blended with a fullerene derivate [6, 6]-phenyl-C61-butyric acid methyl ester (PCBM, electron acceptor). The optical, morphological and photovoltaic properties of cells with a structure of ITO/PEDOT: PSS/P3HT: PCBM/Al has been investigated. We showed the influence of the ambient atmosphere during weighing of compounds or during solution processing. We also studied many parameters such as the active layer thickness, the polymer molecular weight, the solvent nature and the spinning acceleration time. We studied the effect of solvent and thermal annealing treatment on the performance of organic solar cells. The power conversion efficiency was significantly improved by insertion of a layer PEDOT: PSS qualified as ?high conductivity grade?. This specific PEDOT: PSS limits the annealing temperature at 120°C since it dramatically decomposes at higher temperature. The addition of an ultra-thin LiF layer (1 nm) improved significantly the performances. We studied the potential of crosslinkable molecules as active layer: polythiophene and perylene derivatives with specific crosslinkable moities in order to improve the durability of devices. These molecules were able to crosslink by sol-gel method or UV- irradiation. However, the power conversion efficiency of cells was extremely low due to the attack of ITO by acid or due to catalysts involved
Magnin, Delphine. "Inclusion des molécules bioactives dans une matrice polyionique à base de chitosane et de xanthane". Thèse, Université de Sherbrooke, 2004. http://savoirs.usherbrooke.ca/handle/11143/1829.
Testo completoFarès, Mohamed. "Calcul ab initio en base d'orbitales de type Slater et hydrogenoïde : cas des molécules linéaires". Nancy 1, 1994. http://www.theses.fr/1994NAN10089.
Testo completoTonelli, Giovanni. "Systèmes organisés à base de molécules hybrides lipide-nucléotides pour la délivrance des acides nucléiques". Thesis, Bordeaux 2, 2013. http://www.theses.fr/2013BOR22097/document.
Testo completoGene therapy is a molecular medicine and a very powerful tool for the treatment of several diseases such as inherited disorder and cancer. Nucleic acids must penetrate into cells in order to interact with their genetic material. Currently the main limitation to the application of this treatment towards clinics is the lack of robust, safe and efficient gene delivery vectors. The two major classes of vectors are those based on recombinant viruses and those based on non-viral systems. Viral vectors are the most efficient and used in several clinical trials, however they can elicit a strong immune reaction and they possess high cost of production. Non-viral vectors are less immunogenic and can be easily produced on a large scale. A large variety of both cationic lipids and polymers have been developed due to their ability to interact spontaneously with negatively charged nucleic acids to form complexes. However these positively charged complexes can present some toxicity due their non-specific interaction with cell membranes and seric proteins. This is the main limitation for their clinical use. For this purpose, new vectors, neutral or anionic, have to be developed in order to diminish the cytotoxicity and increase the circulation time. Nucleotide-lipids (NLs) are bio-inspired amphiphilic hybrid molecules composed of a hydrophilic nucleotidic moiety and a hydrophobic lipophilic moiety. These molecules are able to self-assembly to form supramolecular structures which possess particular physico-chemical properties due to the chemistry of their polar head. These molecules can interact with a nucleic acid by Watson-Crick base pair interactions, however they are not sufficiently strong to form a stable complex that can be used for a biological application. A new chemical family of hybrid amphiphile, amino acid-nucleotide-lipids (ANLs), has been developed in order to increase the interactions and the stability of the complex thank to the presence of the amino acid on the polar head. Herein, we have synthesized novel amino acid-nucleotide-lipids, presenting phenylalanine (or glycine) and thymidine residues and saturated (dimiristoyl) or unsaturated (dioleoyl) diacyl glycerol lipid. The morphology and the structural organization of the supramolecular objects formed by these molecules was studied by dynamic light scattering (DLS), cryo-electron microscopy (cryo-TEM) and small angle X-ray scattering (SAXS). These studies allowed investigating the relation between the chemical structure and the physic-chemical properties. The amino acids, inserted at the 5′ position of the nucleotide-lipids, stabilize multilamellar systems, whereas unilamellar vesicles are formed preferentially in the case of nucleotide-lipids. Both NLs and ANLs exhibit weak interactions with complementary polyA RNA as revealed by isothermal titration calorimetry (ITC) investigations, however they are not sufficiently strong to form a stable complex that can be used for a biological application. The use of multivalent cations, such as Ca2+, which bridge the phosphate groups on the lipid polar heads with those of the backbone of nucleic acids, to form ternary complexes, has been investigated by SAXS. Finally, a structural study, by DLS and cryo-TEM of NLs aggregates in aqueous solutions as a function of ionic strength and surfactant concentration, has been conducted in order to investigate the different morphologies of the systems
Varlet, Alice-Anaïs. "Analyse fonctionnelle du remodelage des structures à base d'actine qui dirigent la division cellulaire par le complexe chaperon HSPB8-BAG3". Doctoral thesis, Université Laval, 2018. http://hdl.handle.net/20.500.11794/35459.
Testo completoChanges in cell shape are essential to key cellular processes that determine the cell fate, including cell division. They are orchestrated by the remodeling of mechanosensitive actin-based structures guiding cellular tension. Recent data suggest that protein quality control may contribute to the spatiotemporal remodeling of actin-based structures through protein sequestration, recycling and degradation mechanisms. Incidentally, the molecular chaperones of the HSPB family appearas modulatorof actin-based structures under physiological processes. These proteins are known to sequester damaged cellular constituents to prevent their toxic aggregation during proteotoxic stress. Whilst their implications in human pathologies have been clearly established, their mode of action is still poorly understood. The work presented in this thesis addresses the central hypothesis that the chaperone complex formed by HSPB8 and its co-chaperone BAG3 would facilitate the remodeling of actin-based structures, which is deemed instrumental for proper mitotic progression. We have shown that during mitosis, BAG3, in a manner requiring its association with HSPB8, facilitates mitotic rounding, spindle positioning and accurate chromosomes segregation. We further showed that depletion of HSPB8 or BAG3 silencing also interferes with disassembly of the contractile actomyosin ringduring cytokinesis, thereby impairing daughter cells abscission. Such an effect is correlated with accumulation of multinucleated cells, a defect which is corrected by drugs that normalize actin dynamics in HSPB8-depleted cells. These results established a cause-effect relationship between deregulation of actin dynamics and the cell division defects induced by HSPB8 silencing. Further, we found that such a phenotypecan be rescued by rapamycin, a drug that stimulates autophagy, while itis recapitulated in control cells by inhibitors of autophagic degradation. These results, and others presented in this thesis, suggest that the regulation of cell shape remodellingby HSPB8-BAG3 may involve their function in the selective targeting of proteins for autophagic degradation. Finally, evidence was obtained that during mitosis, like during cytokinesis, HSPB8-BAG3 would act by limiting branched actin polymerization. We found that HSPB8-BAG3 can modulate mitotic rounding and the dynamics of an Arp2/3-dependent subcortical actin pool that contributes to spindle positionning, by restrictingthe activity of HDAC6 deacetylase maybe on its target cortactin, both having a role in selective autophagy processes. Together, this work contributed to a better understanding of the mechanisms by which the chaperone complex HSPB8-BAG3 would facilitate transitions in cellshape during cell division and uncovered novel targets of HSPB8-BAG3 that may be implicated in the development of human disorders associated with deregulation of the chaperon complex, notably cancer.
Zhu, Zhenyu. "Développement de nouveaux outils analytiques à base d'acides nucléiques aptamères pour la détection de petites molécules". Phd thesis, Université de Grenoble, 2012. http://tel.archives-ouvertes.fr/tel-00770171.
Testo completoChen, Yani. "Dispositifs hybrides à base de carbone : fonctionnalisation de nanotubes et de graphène avec des molécules actives". Thesis, Université Grenoble Alpes (ComUE), 2016. http://www.theses.fr/2016GREAY025/document.
Testo completoIn the frame of the intense research on electronics beyond CMOS, molecular electronics offers the versatility of organic chemistry in order to tailor new functions combining optical and electronic specifications, while accessing the quantum confined regime intrinsic to small molecules. As 1D conductors, carbon nanotubes bridge the gap between small molecules electronics and semiconductor technology with great promises while being a playground for organic chemistry. Beyond miniaturization, they offer the opportunity to design new devices from accurate sensors to optoelectronic and quantum devices. However most studies focus on sensor or photovoltaic applications and thus involve a macroscopic assembly of nanotubes. This averages the excitation transfers, which prevents access to their fundamental mechanisms. This requires the design of individual carbon nanotube based functional devices. For this issue double wall carbon nanotubes have many advantages over simple SWNTs. In general, they exhibit higher stability, which can be a substantial help in high-current and high-field experiments. They realize a core-shell system: their concentric structure suggests its use for independent doping or functionalization of inner and outer tubes.In this PhD project, we demonstrate field effect transistors based on hybrid systems of individual double wall carbon nanotubes and optically sensitive molecule.We first introduce the method for making individual double wall carbon nanotube field effect transistors (DWNT FETs), which are then characterized both optically and electrically. We also studied the electron phonon coupling in the DWNT system by Raman spectroscopy with electrostatic gating. The inner metallic tube is also affected by the electrostatic gate and shows dramatic changes of the overall Raman signature.We then functionalized non covalently two kinds of optically sensitive molecules to DWNT and graphene FETs (Terpyridine Osmium complex and Zinc(II) metalloporphyrin). The hybrids are characterized both optically and electrically. Charge transfer between DWNTs and molecules plays as a chemical gating which can be detected by Raman spectroscopy as well as electrical transport measurements, which indicates that the DWNT FETs can be utilized for molecular sensing. Light excitation of the molecules leads to doping of the hybrids and reveals the coupling between the nanotube walls.Moreover, we realized wavelength dependent optical gating on the hybrid device, detected by both Raman spectroscopy and electrical transport measurements at both room temperature and helium temperature. The optical control of the hybrids’ electronic behavior will be elucidated in terms of photo-induced charge transfer between the grafted molecules and the DWNT component. As a consequence, this hybrid FETs can be used as an optically controlled memory down to single electron transfers at low temperature
Metri, Noura. "Elaboration de molécules pi-conjuguées à base de triphénylamine pour la réalisation de dispositifs photovoltaïques hybrides sensibilisés". Thesis, Cergy-Pontoise, 2011. http://www.theses.fr/2011CERG0521/document.
Testo completoSolid state dye-sensitized solar cells (ssDSSC) are considered as an emerging technology in order to replace conventional silicon solar cells or even those using liquid electrolyte. In order to improve the performance of ssDSSC devices, we were interested by the development of star-shaped molecules derived from thieno[3,2-b]thiophene unit and triphenylamine core.Two series of new substituted triphenylamine (TPA) derivatives with thiophene and thieno[3,2-b]thiophene units (with and without nonyl group C9H19) were synthesized in a combinatorial manner. These compounds were obtained by Stille or Suzuki coupling with a yield between 11% and 37% (from six to ten steps).In order to determine the properties of these compounds, thermal, optical and electrochemical characterizations were carried out. The measurements by thermogravimetric analysis (TGA) showed a high stability of the compounds above 340°C. Differential thermal analysis (DSC) was used to determine the glass transition temperature (Tg) where the highest reaching 57°C. The optical and electronic gaps were determined by UV-Visible absorption ( we found from 2.87 eV to 2.41 eV in film) or cyclic voltammetry (we found from 3.26 eV to 2.60 eV). The energy levels of HOMO and LUMO were also determined by cyclic voltammetry. They showed adequate levels especially for HOMO levels (ideally HOMO between the dye and that of the cathode) for a photovoltaic application. Finally, hole mobility have shown encouraging results and promising ranging from 10-3 cm2.V-1.s-1 and 1 cm2.V-1.s-1.The theoretical study of these molecules was also carried out using molecular modeling as B3LYP. The energy levels (HOMO and LUMO), the optical gaps, and the energy of internal reorganization (giving an idea of the theoretical charges mobility) have the seam trend overlap the experimental data.The photovoltaic performance of these compounds was performed. An efficiency of 0.5% (not optimized results) has been obtained for the best of them. This efficiency was sustainable after one year. The pore filling ratio of this compound in TiO2 reached from 62 to 83%.Keywords : Solid state dye-sensitized solar cells (ssDSSC), triphenylamine, thieno[3,2-b]thiophene, thiophene, molecular glasses, theoretical calculations, pore filling
Jamshidian, Majid. "Inclusion et libération de molécules antioxydantes dans un emballage à base d’Acide Poly Lactique en contact alimentaire". Thesis, Vandoeuvre-les-Nancy, INPL, 2011. http://www.theses.fr/2011INPL109N/document.
Testo completoActive packaging generates longer shelf-life foods, lower usage of additives and preservatives in food formulations, higher protection of flavors and higher food qualities. Antioxidant controlled release from packaging provides longer food stability (reduced lipid oxidation) by continuously liberating antioxidants at food surface. The overall objective of the present work was to study the suitability of Poly Lactic Acid (PLA, biodegradable polymer industrially produced) as active packaging. We chose various synthetic or natural antioxidants including alpha-tocopherol, Ascorbyl palmitate, BHA, BHT, Propyl gallate and TBHQ to produce the antioxidant packaging. Firstly, the mode of incorporation of these antioxidants in PLA matrix and also their potential effects on diverse structural, thermal, mechanical and barrier properties of PLA were investigated. The release study of antioxidants was accomplished from PLA-antioxidants films into three food simulants, i.e. 95%, 50%, and 10% ethanol at two temperatures (20°C and 40°C). The results showed that PLA has the capability for being as a suitable carrier for antioxidant-active packaging for some food products. Finally, a mathematical model based on quantitative structure property relationships (QSPR) was developed to predict antioxidant diffusion in food simulant/ active packaging system
Schott, Marc-Alexandre. "Encapsulation moléculaire de molécules actives hydrophobes par des polymères amphiphiles aléatoires à base de poly(acide diméthylmalique)". Thesis, Montpellier 1, 2012. http://www.theses.fr/2012MON13510/document.
Testo completoLots of drugs meet some problems because of their poor water-solubility : poor bioavailability, desactivating metabolization, side effects. To overcome these problems, some amphiphilic polyelectrolytes have already been studied. They increased the apparent water-solubility of hydrophobic compounds, but were toxic or not degradable, thus could not be eliminated from the body. In this work, we describe the synthesis of various substituted malolactones. Anionic ring opening copolymerization of these lactones yielded random amphiphilic polyanions with varying and controlled hydrophobization ratio and aliphatic and aromatic side chains with different lengths. These polymers increase the apparent water-solubility of hydrophobic compounds. A synergy between hydrophobic and electrostatic interactions has been demonstrated when the compound is cationic. The apparent solubility of anti-infectious drugs could thus be increased by several orders of magnitude. Under intravenous injection conditions (NaCl 9 g.L-1 and pH = 7,5), these polymers form preferentially intramolecular micelles, which are not sensitive to dilution effects. As a consequence, such a drug transport system would yield no premature release. Being also degradable, these polymers could release the drug and be eliminated from the body. They meet all main physico-chemical criteria to become a drug transport system
Marzouk, Samir. "Synthèse et caractérisation de molécules en haltère à base de phtalocyanines pour l’élaboration de cellules solaires organiques". Thesis, Strasbourg, 2018. http://www.theses.fr/2018STRAE006/document.
Testo completoThis work reports a series of dumbbell-shaped molecules based on phthalocyanine with an electro-donating character, to be used in organic solar cells. More particularly, the molecules are fully-conjugated triads, made of two zinc phthalocyanine fragments separated by a rigid central dye of different nature (derivative of benzothiadiazole, isoindigo or diketopyrrolopyrrole). The synthesis of the materials was optimized by varying the type of the cross-coupling reactions. The properties of the molecules (absorption, energy levels, structure, charge transport and photovoltaic) were investigated as function of the nature of the central dye and the peripheral ramified chains on the phthalocyanine fragments
Piras, Patrick. "Développement et exploitation d'une base de données moléculaire pour la séparation d'énantiomères par chromatographie liquide". Aix-Marseille 3, 1994. http://www.theses.fr/1994AIX30097.
Testo completoNdeboko, Bénédicte. "Développement de nouvelles stratégies antisens à base de PNAs (Peptide Nucleic Acide) pour le traitement des hépatites B chroniques". Lyon 1, 2006. http://www.theses.fr/2006LYO10246.
Testo completoGiving the partial efficacy of nucleoside analogues, novel approaches against chronic hepatitis B virus (HBV) infection need to be developed. Thus, Peptide Nucleic Acid (PNAs), a novel generation of antisense agents, appears of particular value for HBV therapy. We have evaluated the capacity of the PNA to inhibit viral replication in vitro and in vivo in DHBV-infected duck model. Because the major problem of their therapeutic application is their poor intracellular penetration, we have used the PNA coupled to cell penetrating peptide (CPP). First, we have optimized the administration route and show that intravenous route led to a better liver delivery of PNA that intraperitoneal route. We provided here the first evidence that CPP-PNA conjugate and CPPs themselves inhibit viral replication suggesting their usefulness for HBV therapy. Our results also demonstrate that the choice of CPPs used as a vehicle for delivery plays an important role in the specificity and inhibition of viral replication
Chiorescu, Irinel. "Effets quantiques magnétiques dans deux cas limites : molécules à haut spin et à bas spin". Université Joseph Fourier (Grenoble), 2000. http://www.theses.fr/2000GRE10198.
Testo completoIsnard, Olivier. "Rôle des éléments interstitiels sur les alliages pour aimants permanents à base d'éléments de terre rare et de fer : synthèse, étude structurale, analyse spectroscopique en relation avec les propriétés magnétiques". Université Joseph Fourier (Grenoble), 1993. http://www.theses.fr/1993GRE10209.
Testo completo