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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.
11

Synthèse de générateurs de photoacides activables par absorption biphotonique pour la microfabrication à trois dimensions / Synthesis of two-photon activable photoacid generators for three dimensions microfabrication

Vergote, Thomas 03 June 2014 (has links)
Depuis les années 60, la génération d’acide fort de Brönsted par un processus photoinduit à un photon est utilisée dans des nombreux domaines de recherche de plus en plus nombreux. Cependant, de tels acides peuvent-être facilement obtenus par voie biphotonique ce qui présente de nombreux avantages comme par exemple : une meilleure réactivité via une excitation direct du photoacide, l’utilisation possible d’une atmosphère non contrôlée, l’utilisation de microlasers à impulsions sub-nanosecondes peu couteux, mais aussi l’augmentation de la résolution spatiale des micro-objets 3D fabriqués. La génération d’acide se fait généralement par transfert d’électron entre un sensibilisateur et un générateur de photoacide (PAG). Une approche prometteuse consiste à associer, sur une même molécule, un PAG et un chromophore actif à deux photons. Il a donc semblé intéressant de développer de nouveaux PAG capables, par excitation biphotonique, d’amorcer directement la photopolymérisation. Nous avons choisi de préparer des systèmes capto-datifs stilbéniques, de nature neutre ou ionique. Aussi, une série de PAG neutres substitués par des groupements diphénylamino- donneur et iminosulfonates -cyanés accepteurs a été synthétisée. Nous avons également commencé, mais non achevé, la synthèse de PAG neutres portant des groupements iminosulfonates -trifluorométhylés. Puis, nous avons cherché à synthétiser des PAG ioniques substitués soit par un groupement éthoxy soit par un groupement diphénylamino soit par un groupement julolidine. Néanmoins, la dernière étape de la synthèse est pour l’instant un verrou synthétique. / Since the 60’s, the generation of strong Brönsted acids by a one-proton photoinduced process has been used in more and more research areas. Recently, it has been shown, that such acids are easily obtained by a two-photon process. This offers many advantages such as: i) a better reactivity owing to a direct excitation of the photoacid, ii) the possible use of a non-controlled atmosphere, iii) the use of inexpensive microlasers with sub-nanosecond impulsions, iv) the increase of spatial resolution in 3D microfabrication. The acid generation generally proceeds through a photo-induced electro transfer from an excited sensitizer to the photoacid generator (PAG). A promising approach should be the introduction on a single molecule of both a PAG and a two-photon active chromophore moiety. In this context, we have developed new PAGs able to initiate photopolymerisation through a two-photon activation process. The syntheses were focused on stilbenic push-pull systems having either a neutral or an ionic nature. A series of neutral PAGs bearing a diphenylamino donor group and an α-cyano iminosulfonate acceptor moiety has been synthesized. The preparation of neutral PAGs bearing iminosulfonate α-trifluoromethylated groups were not yet completed. The syntheses of ionic PAGs substituted by an ethoxy group, a diphenylamino group or a julolidine one, could not be completed either.
12

Investigating New Guaiazulenes and Diketopyrropyrroles for Photonic Applications

Ghazvini Zadeh, Ebrahim 01 January 2015 (has links)
?-Conjugated systems have been the focus of study in recent years in order to understand their charge transport and optical properties for use in organic electronic devices, fluorescence bioimaging, sensors, and 3D optical data storage (ODS), among others. As a result, several molecular building blocks have been designed, allowing new frontiers to be realized. While various successful building blocks have been fine-tuned at both the electronic and molecular structure level to provide advanced photophysical and optoelectronic characteristics, the azulene framework has been under-appreciated despite its unique electronic and optical properties. Among several attributes, azulenes are vibrant blue naturally occurring hydrocarbons that exhibit large dipolar character, coupled with stimuli-responsive behavior in acidic environments. Additionally, the non-toxic nature and the accompanying eco-friendly feature of some azulenes, namely guaiazulene, may set the stage to further explore a more "green" route towards photonic and conductive materials. The first part of this dissertation focuses on exploiting guaiazulene as a natural building block for the synthesis of chromophores with varying stimuli-responsiveness. Results described in Chapter 1 show that extending the conjugation of guaiazulene through its seven-membered ring methyl group with aromatic substituents dramatically impacts the optical properties of the guaiazulenium carbocation. Study of these ?–stabilized tropilium ions enabled establishing photophysical structure-property trends for guaiazulene-terminated ?-conjugated analogs under acidic conditions, including absorption, emission, quantum yield, and optical band gap patterns. These results were exploited in the design of a photosensitive polymeric system with potential application in the field of three dimensional (3D) optical data storage (ODS). Chapter 2 describes the use of guaiazulene reactive sites (C-3 and C-4 methyl group) to generate a series of cyclopenta[ef]heptalenes that exhibit strong stimuli-responsive behavior. The approach presents a versatile route that allows for various substrates to be incorporated into the resulting cyclopenta[ef]heptalenes, especially after optimization that led to devising a one-pot reaction toward such tricyclic systems. Examining the UV-vis absorption profiles in neutral and acidic media showed that the extension of conjugation at C(4) of the cyclopenta[ef]heptalene skeleton results in longer absorption maxima and smaller optical energy gaps. Additionally, it was concluded that these systems act as sensitizers of a UV-activated (< 300 nm) photoacid generator (PAG), via intermolecular photoinduced electron transfer (PeT), upon which the PAG undergoes photodecomposition resulting in the generation of acid. In a related study, the guaiazulene methyl group at C-4 was employed to study the linear and nonlinear optical properties of 4-styrylguaiazulenes, having the same ?–donor with varying ?-spacer. It was realized that the conjugation length correlates with the extent of bathochromic shift of the protonated species. On the other hand, a trend of decreasing quantum yield was established for this set of 4-styrylguaiazulenes, which can be explained by the increasingly higher degree of flexibility. The second part of this dissertation presents a comprehensive investigation of the linear photophysical, photochemical, and nonlinear optical properties of diketopyrrolopyrrole (DPP)-based derivatives, including two-photon absorption (2PA), femtosecond transient absorption, stimulated emission spectroscopy, and superfluorescence phenomena. The synthetic feasibility, ease of modification, outstanding robustness, and attractive spectroscopic properties of DPPs have motivated their study for fluorescence microscopy applications, concluding that the prepared DPP's are potentially suitable chromophores for high resolution stimulated emission depletion (STED) microscopy.

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