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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
91

Approche théorique de la compréhension de la réactivité de carbènes N-Hétérocycliques vis-à-vis de systèmes (méth)acryliques. Application en polymérisation / Theoretical approach for the comprehension of the N-Heterocyclic carbene’s reactivity to the (meth)acryliques systems. Application for the polymerization

Bourichon, Damien 01 December 2015 (has links)
L’objectif principal de cette thèse était de comprendre par une approche conjointe théorie/expérience des réactions de polymérisation de monomères polaires, plus particulièrement de dérivés (méth)acryliques, réactions organocatalysées par des carbènes N-Hétérocycliques (NHC) utilisés seuls ou associés à une molécule organique (alcool) ou à un acide de Lewis. Pour cela un travail de rationalisation des effets électroniques et stériques apportés par le carbène a été réalisé à la fois sur les premières étapes du mécanisme de polymérisation par la théorie de la fonctionnelle de la densité (DFT) mais également sur les mécanismes potentiellement concurrents (cyclo-dimérisation) par deux méthodes théoriques: la DFT et la dynamique moléculaire (MD). L’ajout d’une molécule tierce comme un alcool ou un acide de Lewis (borane ou silane) a également été étudié théoriquement en détail afin de mieux comprendre l’effet de cette association sur la nature du mécanisme privilégié et sur l’efficacité de la polymérisation. / The main objective of this thesis was to understand, by a joint theoretical/experimental approach, polymerization reactions of polar monomers, especially (meth)acrylic derivatives, organocacatalyzed polymerizations by N-Heterocyclic carbenes (NHC) used alone or in combination with an organic molecule (alcohol) or a Lewis acid. Rationalization of both electronic and steric effects of the carbene was performed on the first steps of the polymerization mechanism by the functional density theory (DFT) and also on potentially competitive mechanisms (cyclodimerization) by two theoretical methods: DFT and molecular dynamics (MD). The addition of a third molecule such as an alcohol or a Lewis acid (borane or silane) has also been theoretically studied in detail in order to better understand the effect of this association on the nature of the privileged pathway and the effectiveness of the polymerization.
92

Synthèse et réactivité de nouveaux complexes des métaux du groupe 13 portés par des ligands carbènes N-hétérocycliques / Synthesis and reactivity of group 13 metals complexes supported by N-heterocyclic carbenes

Schnee, Gilles 15 November 2012 (has links)
Au début de ces travaux, peu d’études avaient été faites sur la complexation des carbènes N-hétérocycliques avec des métaux oxophiles, électropositifs et à hauts degrés d’oxydation tel que les métaux du groupe 13. L’optimisation de voies de synthèse a permis d’étendre le nombre de complexes de types NHC-MIII (M = aluminium, gallium et indium), ainsi qu’à des complexes cationiques. L’association de ces précurseurs avec des NHCs plus encombrés a permis l’observation de réactivités sans précédent (complexes anormaux, paires de Lewis frustrées, dicarbènes N-hétérocycliques). Dans un second temps, la réactivité inhabituelle des ligands NHCs a permis l’isolation d’analogue au réactif de Tebbe, très actifs en méthylénation de dérivés carbonyles. / At the beginning of this work, few studies had been performed on the complexation of N-heterocyclic carbenes with oxophilic metals, in high oxidation states such as group 13 metals. The synthetic routes optimization has extended the number of complexes-type NHC-MIII (M = aluminum, gallium and indium), and the corresponding cationic complexes. The combination of these precursors with sterically congested NHCs allowed the observation of unprecedented reactivities (abnormal complexes, Frustrated Lewis Pairs, N-heterocyclic dicarbenes). In a second step, the unusual reactivity of NHC ligands has allowed the isolation of analogues of the Tebbe’s reagent, formed to be very active in the methylenation of carbonyl compounds.
93

Heteroleptic platinum(II) NHC complexes with a C^C* cyclometalated ligand – synthesis, structure and photophysics

Tronnier, Alexander, Heinemeyer, Ute, Metz, Stefan, Wagenblast, Gerhard, Muenster, Ingo, Strassner, Thomas 10 January 2020 (has links)
Platinum(II) complexes [(NHC)Pt(L)] with various β-diketonate based auxiliary ligands (L: 3-meacac = 3-methylacetylacetonato, dpm = dipivaloylmethanato, dbm = dibenzoylmethanato, mesacac = dimesitoylmethanato, duratron = bis(2,3,5,6-tetramethylbenzoyl)methanato) and a C^C* cyclometalated N-heterocyclic carbene ligand (NHC: dpbic = 1,3-iphenylbenzo[d]imidazol-2-ylidene, dpnac = 1,3-diphenylnaphtho[2,3-d]imidazol-2-ylidene or bnbic = 1-phenyl-3-benzylbenzo[d]imidazol-2-ylidene) were found to show different aggregation and photophysical properties depending on the auxiliary ligand. Eight complexes were prepared from a silver(I)–NHC intermediate by transmetalation, cyclometalation and subsequent treatment with potassium-tert-butanolate and β-diketone. They were fully characterized by standard techniques including ¹⁹⁵Pt NMR. Five complexes were additionally characterized by 2D NMR spectroscopy (COSY, HSQC, HMBC and NOESY). Solid-state structures of five complexes could be obtained and show the tendency of the square-planar compounds to form pairs with different Pt–Pt distances depending on the bulkiness of the substituents at the auxiliary ligand. The result of the photophysical measurements in amorphous PMMA films reveals quantum yields of up to 85% with an emission maximum in the blue region and comparatively short decay lifetimes (3.6 µs). Density functional theory (DFT/TD-DFT) calculations were performed to elucidate the emission process and revealed a predominant ³ILCT/³MLCT character. Organic light-emitting devices (OLEDs) comprising one of the complexes achieved 12.6% EQE, 11.9 lm W⁻¹ luminous efficacy and 25.2 cd A⁻¹ current efficiency with a blue emission maximum at 300 cd m⁻². The influence of an additional hole-transporter in the emissive layer was investigated and found to improve the device lifetime by a factor of seven.

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