La limitation optique (LO) est un processus de protection des détecteurs optiques (yeux, caméras…) vis-à-vis des agressions laser. Le développement rapide de ces derniers aux fréquences des télécommunications a encouragé l’ingénierie moléculaire pour la LO dans cette fenêtre spectrale, en particulier à 1500 nm. Un des principaux mécanismes de la LO est l’absorption multiphotonique et plus particulièrement l’absorption à deux photons (ADP). Il s’agit d’un phénomène d’optique non-linéaire du troisième ordre au cours duquel un électron est promu de l’état fondamental vers l’état excité par absorption simultanée de deux photons. De plus, des travaux récents ont mis en évidence que le phénomène de LO peut être exalté par des processus d’absorption à l’état excité (AEE) induits par ADP. Dans ce contexte, cette thèse décrit la synthèse d’une nouvelle famille de chromophores de type aza-dipyrrométhène de bore (Aza-Bodipy), fonctionnalisés par des groupements donneur ou accepteur d’électrons. Ces molécules ont un comportement de limiteur optique sur toute la gamme spectrale voulue, avec un maximum d’efficacité vers 1300 nm. Les résultats ont été interprétés sur la base de deux phénomènes : l’ADP, suivie de l’AEE pour un procédé d’absorption globale à trois photons. Ces deux processus ont été mesurés séparément et des relations structure-activité ont été établies, afin de rationnaliser les données de LO. L’importance du transfert de charge et la superposition spectrale des deux phénomènes sont alors apparues comme les paramètres clefs à optimiser. En vue d’une application dans un dispositif optique réel, il est nécessaire que les chromophores soient incorporés dans un matériau solide, qui peut être poli et transformé. Ainsi, les composés synthétisés ont été insérés avec succès dans une matrice sol-gel. Pour la première fois, des matériaux de qualité optique ont été réalisés, possédant des propriétés de LO dans l’infra-rouge très performantes et meilleures qu’en solution. / The optical power limiting (OPL) is a protection process of detectors (eyes, cameras…) against laser aggression. The rapid development of frequency-tunable pulsed lasers up to telecommunication wavelengths led to the design of new materials for nonlinear absorption in this spectral range, in particular at 1500 nm. Mutiphotonic absorption, such as the two-photon absorption (TPA) is one of the mechanisms involved in the OPL. TPA is a third order nonlinear phenomenon that promotes a molecule to an excited state by the simultaneous absorption of two photons. Moreover, the overall OPL efficiency can be enhanced by excited state absorption (ESA). In this context, this thesis describes the synthesis of a new family of versatile near infra-red dyes, namely aza-borondipyrromethene (Aza-Bodipy) featuring several sites of functionalization by electro-donating or electro-withdrawing moieties. These molecules present the typical behavior of optical limiters at telecommunication wavelengths, with a maximal efficiency around 1300 nm. OPL curves were interpreted on the basis of two phenomena: TPA, followed by ESA for an overall 2+1 photons absorption. These two processes have been measured independently and structure-activity relationships have been established in order to rationalize OPL experiments. The charge transfer effect and the spectral overlap between TPA and ESA are therefore the key parameters. For practical use of OPL functions, it is required for the chromophores to be introduced into a solid material, which enables polishing and other post-processing. Therefore, Aza-Bodipy dyes have been successfully incorporated to a solid matrix using the sol-gel technique. For the first time, optical quality materials have been prepared featuring OPL properties in the infra-red, which are better than the ones in solution.

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Neste trabalho, são estudadas as alterações das propriedades ópticas lineares e não lineares de soluções de azocompostos devidas aos mecanismos de isomerização e às alterações das propriedades estruturais com a temperatura. A dependência da transição pipi* com a estrutura linear dos azocompostos é notada já nas medidas dos espectros de absorção em função da temperatura para o isômero trans. Através do conhecimento dos níveis de energia e dos tempos de relaxação via isomerização, foi possível obter a dinâmica entre os isômeros cis e trans. As medidas não lineares forneceram propriedades interessantes associadas aos estados de energia dos compostos. Por exemplo, através de experimentos de varredura-z e de excitação e prova, foi possível ver que os azocompostos apresentam uma alta transparência quando excitados, a qual desaparece com o término da isomerização. Medidas em função do comprimento de onda mostraram que a transparência observada está presente em toda a banda pipi* e não ocorre na banda npi* . Também foi observado que o tempo de isomerização muda de acordo com o comprimento de onda de excitação, o que pode estar relacionado com a superposição das duas bandas. Os resultados obtidos em femtossegundos foram essenciais para descrever o processo dinâmico de fotoisomerização, observado, por completo, através de medidas com varredura-Z em picossegundos e nanossegundos. Essas medidas forneceram os valores das seções de choque dos isômeros cis, que são difíceis de serem quantificadas devido ao curto tempo de vida desse isômero. Além dos resultados ressonantes, foram feitos experimentos de absorção de dois fótons em femtossegundos usando a técnica de varredura-Z. Esses estudos mostraram a dependência das seções de choque de absorção de dois fótons com características estruturais das moléculas, tais como comprimento de conjugação, grupos push-pull e planaridade. Os resultados ressonantes e não ressonantes obtidos em femtossegundos serviram de base para a calibração da técnica de varredura-Z com pulsos de luz branca. Essa técnica se mostrou adequada para a obtenção dos espectros das não linearidades ópticas ressonantes e não ressonantes em uma única medição (de 5 minutos), diminuindo assim flutuações do laser durante o experimento. / This work reports on the temperature dependence of linear and nonlinear properties of azocompounds solutions due to isomerization mechanisms. The dependence of pipi* transitions on the linear structure of azocompounds is already noticeble in the measurements of absorption spectra as function of the temperature for the trans isomer. Knowing the energy levels and the relaxation times through isomerization, it was possible to obtain the exchange dynamics between cis and trans conformations. Nonlinear measurements provided interesting properties associated with the energy levels of de compounds. For exemple, through Z-scan and pumpprobe experiments, it was possible to verify that azocompounds present a high transparency when excited and that this transparency disapears when the izomerization ends. The wavelength change has shown that the observed transparency is present along the complete pipi* band, but not in the npi* band. It was also observed that the isomerization time changes with the exciting wavelength, which may be related to the superposition of both bands. The results obained with femtoseconds pulses were essential to completily describe the photoisomerization process observed with Z-scan measurements using picoseconds and nanoseconds pulses. These measurements provided values of the crosssection of the cis conformation, which are difficult to be quantified due to the short lifetime of this isomer. Besides ressonant results, experiments of two-photon absorption in the femtosecond regime using the Z-scan technique were made. These studies shown the dependence of the two photons absorption cross-section on structural features of molecules such as conjugation length, push-pull groups and planarity. The ressonant and nonressonant results obteined with femtoseconds have provide the calibration of the Z-scan technique with white light pulses. This technique has been found able to obtain the spectra of ressonat and nonressonant nonlinearities in a single measurement (about 5 minutes), diminishing laser fluctuation during the experiment.

Neste trabalho, são estudadas as alterações das propriedades ópticas lineares e não lineares de soluções de azocompostos devidas aos mecanismos de isomerização e às alterações das propriedades estruturais com a temperatura. A dependência da transição pipi* com a estrutura linear dos azocompostos é notada já nas medidas dos espectros de absorção em função da temperatura para o isômero trans. Através do conhecimento dos níveis de energia e dos tempos de relaxação via isomerização, foi possível obter a dinâmica entre os isômeros cis e trans. As medidas não lineares forneceram propriedades interessantes associadas aos estados de energia dos compostos. Por exemplo, através de experimentos de varredura-z e de excitação e prova, foi possível ver que os azocompostos apresentam uma alta transparência quando excitados, a qual desaparece com o término da isomerização. Medidas em função do comprimento de onda mostraram que a transparência observada está presente em toda a banda pipi* e não ocorre na banda npi* . Também foi observado que o tempo de isomerização muda de acordo com o comprimento de onda de excitação, o que pode estar relacionado com a superposição das duas bandas. Os resultados obtidos em femtossegundos foram essenciais para descrever o processo dinâmico de fotoisomerização, observado, por completo, através de medidas com varredura-Z em picossegundos e nanossegundos. Essas medidas forneceram os valores das seções de choque dos isômeros cis, que são difíceis de serem quantificadas devido ao curto tempo de vida desse isômero. Além dos resultados ressonantes, foram feitos experimentos de absorção de dois fótons em femtossegundos usando a técnica de varredura-Z. Esses estudos mostraram a dependência das seções de choque de absorção de dois fótons com características estruturais das moléculas, tais como comprimento de conjugação, grupos push-pull e planaridade. Os resultados ressonantes e não ressonantes obtidos em femtossegundos serviram de base para a calibração da técnica de varredura-Z com pulsos de luz branca. Essa técnica se mostrou adequada para a obtenção dos espectros das não linearidades ópticas ressonantes e não ressonantes em uma única medição (de 5 minutos), diminuindo assim flutuações do laser durante o experimento. / This work reports on the temperature dependence of linear and nonlinear properties of azocompounds solutions due to isomerization mechanisms. The dependence of pipi* transitions on the linear structure of azocompounds is already noticeble in the measurements of absorption spectra as function of the temperature for the trans isomer. Knowing the energy levels and the relaxation times through isomerization, it was possible to obtain the exchange dynamics between cis and trans conformations. Nonlinear measurements provided interesting properties associated with the energy levels of de compounds. For exemple, through Z-scan and pumpprobe experiments, it was possible to verify that azocompounds present a high transparency when excited and that this transparency disapears when the izomerization ends. The wavelength change has shown that the observed transparency is present along the complete pipi* band, but not in the npi* band. It was also observed that the isomerization time changes with the exciting wavelength, which may be related to the superposition of both bands. The results obained with femtoseconds pulses were essential to completily describe the photoisomerization process observed with Z-scan measurements using picoseconds and nanoseconds pulses. These measurements provided values of the crosssection of the cis conformation, which are difficult to be quantified due to the short lifetime of this isomer. Besides ressonant results, experiments of two-photon absorption in the femtosecond regime using the Z-scan technique were made. These studies shown the dependence of the two photons absorption cross-section on structural features of molecules such as conjugation length, push-pull groups and planarity. The ressonant and nonressonant results obteined with femtoseconds have provide the calibration of the Z-scan technique with white light pulses. This technique has been found able to obtain the spectra of ressonat and nonressonant nonlinearities in a single measurement (about 5 minutes), diminishing laser fluctuation during the experiment.

L’objectif de cette thèse consistait à développer des colorants de la famille des polyméthines absorbant dans le proche infrarouge et présentant des propriétés d’optique non-linéaire (ONL) prononcées. De nouveaux chromophores ont été préparés et leurs propriétés spectroscopiques ont été systématiquement étudiées afin d’établir des relations structures-propriétés. Cette stratégie a permis l’identification des facteurs permettant d’exalter la réponse ONL des polyméthines et de prédire leur comportement face à de subtiles modifications structurales. Trois familles de colorants ont été préparées : des monométhines aza-dipyrrométhènes de bore, des heptaméthines symétriques ainsi que des heptaméthines dissymétriques.Dans un premier temps, des aza-bodipys possédant des groupements donneurs périphériques sont synthétisés. Une étude spectroscopique approfondie permet d’identifier les structures présentant une absorption à deux photons importante en vue d’applications en limitation optique aux longueurs d’onde des télécommunications (1500 nm). Le chapitre suivant a pour but de rationaliser les équilibres de la limite cyanine. L’étude de la substitution centrale de nombreux dérivés heptaméthines a permis de moduler leurs propriétés optiques sur une large gamme spectrale et de mettre en évidence une nouvelle structure électronique limite de type bis-dipôle. Parmi cette famille de colorants, des dérivés keto-heptaméthines ont été utilisées en imagerie biologique (cellules et cerveau) par microscopie non-linéaire. Enfin, l’élaboration de structures heptaméthines dissymétriques originales est détaillée dans le dernier chapitre. Ces chromophores ont révélé des propriétés ONL du second ordre idéales pour des applications en modulation électro-optique. / The aim of this thesis consisted in developing dyes from the polymethine family absorbing in the near-infrared (NIR) region and featuring pronounced nonlinear optical (NLO) properties. Several new chromophores have been prepared and their spectroscopic properties have been systematically investigated in order to establish structure-properties relationships. This strategy has permitted the identification of the factors that enhance the NLO response of polymethines and allowed the prediction of their optical behaviour depending on subtle structural modifications. Three families of dyes have been prepared and investigated: boron aza-dipyrro-monomethines (aza-bodipys), symmetrical heptamethines and unsymmetrical heptamethines.In a first time, aza-bodipys possessing electro-donating peripherical substituants has been synthesized. A detailed spectroscopic study allow the identification of structures that present a high two-photon absorption (TPA), towards optical limiting applications at telecommunication wavelengths (1500 nm). The next chapter rationalizes the equilibrium surrounding the cyanine limit. The study of the central substitution of several heptamethines derivatives permitted the fine tuning of their optical properties upon a large spectral region and evidenced a new bis-dipolar electronic structure. Within this dye family, keto heptamethine derivatives has been tested in bio-imaging experiments (living cells and brain) using non-linear microscopy. Finally, the elaboration of original unsymmetrical heptamethines is detailed in the last chapter. These chromophores revealed ideal second order NLO properties for applications in electro-optic modulation.

Cette thèse présente l’étude théorique et expérimentale de la génération et de la mise en forme d’impulsions térahertz (THz). Dans un premier temps, nous avons étudié la génération d’impulsions THz par redressement optique d’impulsions laser femtosecondes intenses dans des cristaux semiconducteurs de ZnTe. Nous avons mis en évidence une forte dépendance de l'efficacité de ce processus de génération avec l'intensité de l'impulsion laser génératrice. Ceci se traduit en particulier par un décalage progressif du spectre vers les basses fréquences et par une évolution anormale de l'énergie THz avec l'intensité laser. Ces comportements résultent d'une combinaison de trois phénomènes : la déplétion de l’impulsion laser au cours de sa propagation dans le cristal, l’absorption de l'onde THz par les porteurs libres créés par absorption à deux photons et une modification de la condition d’accord de phase. Dans un deuxième temps, nous avons développé une approche analytique permettant de générer des impulsions THz de formes particulièrement intéressantes pour les expériences de spectroscopie cohérente ou de contrôle cohérent. Nous avons notamment généré des paires d'impulsions verrouillées en phase, des trains d'impulsions, ainsi que des impulsions THz accordables de grande finesse spectrale. Cette technique repose sur le redressement optique d’impulsions laser femtosecondes mises en forme à l’aide d’un masque à cristaux liquides placé dans le plan de Fourier d’une ligne à dispersion nulle. Afin de démontrer la validité de notre approche, nous avons également développé un programme de simulation qui donne des résultats en très bon accord avec l'expérience. / This thesis deals with the theoretical and experimental study of the generation and shaping of terahertz (THz) pulses. At first, we have studied the generation of THz pulses by optical rectification of intense femtosecond laser pulses in semiconductor ZnTe crystals. We have demonstrated a strong dependence of the efficiency of the generation process with the intensity of the laser pulse. This is evidenced by a progressive shift of the spectrum towards lower frequencies and an abnormal evolution of the THz energy with laser intensity. These behaviors result from a combination of three phenomena: the depletion of the laser pulse during its propagation in the crystal, the absorption of THz wave by free carriers created by two-photon absorption and a change of the phase matching condition. Secondly, we have developed an analytical approach to generate THz shaped pulses particularly interesting for coherent spectroscopy or coherent control. In particular, we have generated phase-locked THz pulses pairs, pulse trains and tunable narrow-band THz pulses. This technique is based on optical rectification of shaped femtosecond laser pulses generated by a liquid crystal Fourier filter. To demonstrate the validity of our approach, we have also developed a program giving results in very good agreement with experiment.

Dans cette thèse, les propriétés optiques de biomolécules importantes ont été étudiées en utilisant une approche théorique et, dans un cas, aussi expérimentale. La Théorie de la fonctionnelle de la densité (DFT) et la timedependent-DFT (TD-DFT) sont les principales méthodes de chimie quantique utilisées dans cette thèse. Plusieurs spectroscopies ont été étudiées (au niveau théorique et, dans certains cas, également au niveau expérimental) : absorption électronique linéaire (absorption à un photon, OPA) et non-linéaire (absorption à deux ou trois photons, TPA et 3PA), dichroïsme circulaire électronique (DCE) et spectroscopie de fluorescence. Les effets de l’environnement, particulièrement importants dans des systèmes biologiques, ont été pris en compte, pour les propriétés de l’état fondamental et des états excités en utilisant une méthode multi-échelles QM/MM appelée Polarizable Embedding (PE). L’échantillonnage des conformations a été pris en compte avec des simulations de dynamique moléculaire (MD) qui sont basées sur la mécanique classique. Deux thématiques ont été étudiées dans cette thèse : le cholestérol et le design in silico de ses analogues fluorescents ainsi que la caractérisation des coudes de type β dans différentes conformations grâce à la simulation des spectres DCE. La simulation de plus d’une spectroscopie a été importante dans l’étude des états excités du cholestérol dans des solutions organiques. Le design in silico a suggéré un nouveau stérol-polyénique (P-stérol) qui montre despropriétés optiques améliorées pour le mécanisme d’excitation à trois photons par rapport au déhydroergostérol (DHE), une sonde du cholestérol déjà très utilisée. Ce nouveau P-stérol a été suggéré pour la synthèse. L’étude des spectres de DCE des coudes β en différentes conformations a mené une double conclusion : même si deux allures de DCE pour les conformations des coudes β étudiées (4) ont été trouvées (dans la majorité des cas), la spectroscopie de DCE doit toujours être associée à d’autres techniques spectroscopiques dans la caractérisation en solution des coudes β. / In this thesis, the optical properties of important biomolecules were studied using a theoretical approach and, in one case, also an experimental one. Density Functional Theory (DFT) and time-dependent-DFT (TD-DFT), were the principal quantum chemical methods adopted in this thesis.Various spectroscopies were studied (theoretically and, in some cases, also experimentally) : linear (one-photon, OPA) and non-linear (two- and three-photon, TPA and 3PA) electronic absorption, electronic circular dichroism (ECD) and fluorescence spectroscopy. The environment effects, which are particularly important in biological systems, were taken into account, for both ground and excited states properties, using a multiscale QM/MM method called Polarizable Embedding (PE). The sampling of conformations was addressed by Molecular Dynamic (MD) simulations based on classical mechanics. Two topics were studied in this thesis: cholesterol and the in-silico design of its fluorescent analogues, and the characterization of β-turns in different conformations by simulations of their ECD spectra in aqueous solutions. The simulation of more than one spectroscopy resulted to be important when studying the electronic excited states of cholesterol in organic solutions. The in-silico design study suggested a novel polyene-sterol (P-sterol) which shows improved optical properties for the three-photon excitation mechanism with respect to dehydroergosterol (DHE), an already widely used cholesterol probe. This new P-sterol was thus suggested for synthesis. The achievement from the study of ECD spectra for different β-turn conformations is two-fold: even if two ECD patterns for the β-turn conformations studied (4) were found (in most of cases), ECD spectroscopy should be always associated with other spectroscopic techniques when trying to characterize the β-turn conformations in solutions.