Di, quadri, octupolar carbo-chromophores for two-photon absorption

Le manuscrit traite de la conception, la synthèse et l'étude des propriétés optiques d'absorption à un et deux photons d'une série de chromophores organiques à systèmes pi-conjugués étendus de la famille des carbo-mères, en s'appuyant sur des résultats préliminaires obtenus par l'équipe avec des carbo-benzènes quadripolaires à substituants fluorényles. Le phénomène d'absorption à deux photons (A2P) présentant une large gamme d'applications dans divers domaines tels que la photothérapie dynamique, le stockage de données, la microfabrication ou la limitation optique, il a fait l'objet de nombreuses études qui ont permis de définir des relations structure-propriétés (RSP) pour l'élaboration de systèmes efficaces, pour lesquelles des dérivés carbo-benzéniques répondent à plusieurs critères a priori. Le travail réalisé dans le cadre de cette thèse concerne essentiellement la synthèse et la caractérisation de carbo-benzènes dipolaires, quadripolaires et octupolaires fonctionnels. L'étude des propriétés optiques linéaires et non-linéaires des cibles "carbo-chromophores" isolées, réalisée en collaboration avec Gabriel Ramos-Ortiz, CIO, Mexique, est également présentée. Le premier chapitre, bibliographique, est divisé en deux parties. La première présente l'état de l'art en optique non linéaire, en particulier du 3ème ordre pour l'absorption à deux photons (A2P). Les applications de l'A2P, les techniques de mesures de section efficace et les RSP pour la conception de chromophores efficaces y sont détaillées. La deuxième partie dresse un état de l'art sur les molécules carbo-mères en détaillant leur synthèse et leurs propriétés. Le deuxième chapitre décrit des résultats de préparation et d'étude de carbo-benzènes quadripolaires. Il est divisé en trois parties. La première décrit la préparation de carbo-benzènes à substituants trifluorotolyle ainsi que l'étude de leurs propriétés d'absorption à un photon, de solubilité, d'accepteur d'électrons (par voltammétrie) et d'auto-assemblage sur surface (par imagerie STM). La deuxième partie présente la synthèse et l'étude comparative des propriétés d'absorption à un et deux photons de bis-dialkylthiényléthynyl-carbo-benzènes et de leur molécule parente à cœur simplement benzénique, les propriétés optiques ayant été étudiées en collaboration avec Gabriel Ramos-Ortiz. La troisième partie envisage des chromophores à cœur dicétopyrrolopyrrole, un motif chromophore classique en A2P, en vue de la synthèse de dérivés à deux substituants carbo-benzéniques. Le troisième chapitre se concentre sur la mise au point d'une nouvelle voie de synthèse de carbo-benzènes octupolaires faisant intervenir une stratégie de macrocyclisation inédite de type [6+6+6], l'objectif restant l'étude des propriétés d'A2P des cibles. Trois carbo-benzènes, à trois substituants fluorényléthynyle ou dialkylthiényléthynyle ont ainsi été préparés et caractérisés. Le quatrième chapitre aborde le défi de la synthèse de carbo-benzènes dipolaires portant des substituants donneurs (de type 4-alkoxy- ou 4-amino-phényles) et accepteurs (de type 4-nitro ou 4-cyano-phényles) en positions para. Les différentes stratégies de synthèse envisagées et les résultats obtenus sont détaillés.The manuscript deals with the design, synthesis and study of optical properties of one- and two-photon absorption in a series of organic chromophores with extended pi-conjugated systems of the carbo-mers family, based on preliminary results obtained by the group for quadrupolar carbo-benzenes with fluorenyl substituents. The phenomenon of two-photon absorption (A2P) presenting a wide range of applications in various fields such as dynamic phototherapy, data storage, microfabrication or optical limitation, it has been the subject of numerous investigations which have allowed the establishment of structure-property relationships (SPRs) for the development of efficient systems, for which carbo-benzene derivatives meet several criteria a priori. Within the framework of this thesis, the work mainly concerns the synthesis and characterization of dipolar, quadrupolar and octupolar functional carbo-benzenes. The study of linear and non-linear optical properties of the isolated "carbo-chromophore" targets, performed in collaboration with Gabriel Ramos-Ortiz, CIO, Mexico, is also presented. The first chapter, bibliographical in nature, is divided into two parts. The first one presents the state of the art in nonlinear optics, in particular at the 3rd order for two photon absorption (A2P). The applications of A2P, techniques of cross-section measurement, and RSPs for the design of efficient chromophores are detailed. The second part provides a state of the art on carbo-meric molecules by giving an overview of their synthesis and properties. The second chapter describes results on the preparation and study of quadrupolar carbo- benzenes. It is divided into three parts. The first one describes the preparation of trifluorotolyl-substituted carbo-benzenes as well as the study of their properties of one-photon absorption, solubility, electro-chemical reductibility (by voltammetry) and self-assembly on surface (by STM imaging). The second part presents the synthesis and comparative study of one- and two-photon absorption properties of bis-dialkylthienylethynyl-carbo-benzenes and their parent molecule with a simple benzene core, the optical properties having been studied in collaboration with Gabriel Ramos-Ortiz. The third part envisages chromophores with a diketopyrrolopyrrole core, a classical chromophoric unit in A2P, aiming at the ultimate synthesis of derivatives with two carbo-benzene substituents. The third chapter focuses on the development of a new route for the synthesis of octupolar carbo-benzenes based on a novel macrocyclization strategy of the [6 + 6 + 6] type, the objective remaining to study of A2P properties of the targets. Three carbo-benzenes, with three fluorenylethynyl or dialkylthienylethynyl substituents were thus prepared and characterized. The fourth chapter addresses the challenge of the synthesis of dipolar carbo-benzenes carrying donor substituents (of 4-alkoxy- or 4-amino-phenyl type) and acceptor (of 4-nitro or 4-cyano-phenyl type) in para positions. The different synthesis strategies that have been envisaged and the obtained results are detailed

Carbo-chromophores di, quadri, octupolaires pour l'absorption à deux photons

The manuscript deals with the design, synthesis and study of optical properties of one- and two-photon absorption in a series of organic chromophores with extended pi-conjugated systems of the carbo-mers family, based on preliminary results obtained by the group for quadrupolar carbo-benzenes with fluorenyl substituents. The phenomenon of two-photon absorption (A2P) presenting a wide range of applications in various fields such as dynamic phototherapy, data storage, microfabrication or optical limitation, it has been the subject of numerous investigations which have allowed the establishment of structure-property relationships (SPRs) for the development of efficient systems, for which carbo-benzene derivatives meet several criteria a priori. Within the framework of this thesis, the work mainly concerns the synthesis and characterization of dipolar, quadrupolar and octupolar functional carbo-benzenes. The study of linear and non-linear optical properties of the isolated "carbo-chromophore" targets, performed in collaboration with Gabriel Ramos-Ortiz, CIO, Mexico, is also presented. The first chapter, bibliographical in nature, is divided into two parts. The first one presents the state of the art in nonlinear optics, in particular at the 3rd order for two photon absorption (A2P). The applications of A2P, techniques of cross-section measurement, and RSPs for the design of efficient chromophores are detailed. The second part provides a state of the art on carbo-meric molecules by giving an overview of their synthesis and properties. The second chapter describes results on the preparation and study of quadrupolar carbo- benzenes. It is divided into three parts. The first one describes the preparation of trifluorotolyl-substituted carbo-benzenes as well as the study of their properties of one-photon absorption, solubility, electro-chemical reductibility (by voltammetry) and self-assembly on surface (by STM imaging). The second part presents the synthesis and comparative study of one- and two-photon absorption properties of bis-dialkylthienylethynyl-carbo-benzenes and their parent molecule with a simple benzene core, the optical properties having been studied in collaboration with Gabriel Ramos-Ortiz. The third part envisages chromophores with a diketopyrrolopyrrole core, a classical chromophoric unit in A2P, aiming at the ultimate synthesis of derivatives with two carbo-benzene substituents. The third chapter focuses on the development of a new route for the synthesis of octupolar carbo-benzenes based on a novel macrocyclization strategy of the [6 + 6 + 6] type, the objective remaining to study of A2P properties of the targets. Three carbo-benzenes, with three fluorenylethynyl or dialkylthienylethynyl substituents were thus prepared and characterized. The fourth chapter addresses the challenge of the synthesis of dipolar carbo-benzenes carrying donor substituents (of 4-alkoxy- or 4-amino-phenyl type) and acceptor (of 4-nitro or 4-cyano-phenyl type) in para positions. The different synthesis strategies that have been envisaged and the obtained results are detailed.Le manuscrit traite de la conception, la synthèse et l'étude des propriétés optiques d'absorption à un et deux photons d'une série de chromophores organiques à systèmes pi-conjugués étendus de la famille des carbo-mères, en s'appuyant sur des résultats préliminaires obtenus par l'équipe avec des carbo-benzènes quadripolaires à substituants fluorényles. Le phénomène d'absorption à deux photons (A2P) présentant une large gamme d'applications dans divers domaines tels que la photothérapie dynamique, le stockage de données, la microfabrication ou la limitation optique, il a fait l'objet de nombreuses études qui ont permis de définir des relations structure-propriétés (RSP) pour l'élaboration de systèmes efficaces, pour lesquelles des dérivés carbo-benzéniques répondent à plusieurs critères a priori. Le travail réalisé dans le cadre de cette thèse concerne essentiellement la synthèse et la caractérisation de carbo-benzènes dipolaires, quadripolaires et octupolaires fonctionnels. L'étude des propriétés optiques linéaires et non-linéaires des cibles "carbo-chromophores" isolées, réalisée en collaboration avec Gabriel Ramos-Ortiz, CIO, Mexique, est également présentée. Le premier chapitre, bibliographique, est divisé en deux parties. La première présente l'état de l'art en optique non linéaire, en particulier du 3ème ordre pour l'absorption à deux photons (A2P). Les applications de l'A2P, les techniques de mesures de section efficace et les RSP pour la conception de chromophores efficaces y sont détaillées. La deuxième partie dresse un état de l'art sur les molécules carbo-mères en détaillant leur synthèse et leurs propriétés. Le deuxième chapitre décrit des résultats de préparation et d'étude de carbo-benzènes quadripolaires. Il est divisé en trois parties. La première décrit la préparation de carbo-benzènes à substituants trifluorotolyle ainsi que l'étude de leurs propriétés d'absorption à un photon, de solubilité, d'accepteur d'électrons (par voltammétrie) et d'auto-assemblage sur surface (par imagerie STM). La deuxième partie présente la synthèse et l'étude comparative des propriétés d'absorption à un et deux photons de bis-dialkylthiényléthynyl-carbo-benzènes et de leur molécule parente à cœur simplement benzénique, les propriétés optiques ayant été étudiées en collaboration avec Gabriel Ramos-Ortiz. La troisième partie envisage des chromophores à cœur dicétopyrrolopyrrole, un motif chromophore classique en A2P, en vue de la synthèse de dérivés à deux substituants carbo-benzéniques. Le troisième chapitre se concentre sur la mise au point d'une nouvelle voie de synthèse de carbo-benzènes octupolaires faisant intervenir une stratégie de macrocyclisation inédite de type [6+6+6], l'objectif restant l'étude des propriétés d'A2P des cibles. Trois carbo-benzènes, à trois substituants fluorényléthynyle ou dialkylthiényléthynyle ont ainsi été préparés et caractérisés. Le quatrième chapitre aborde le défi de la synthèse de carbo-benzènes dipolaires portant des substituants donneurs (de type 4-alkoxy- ou 4-amino-phényles) et accepteurs (de type 4-nitro ou 4-cyano-phényles) en positions para. Les différentes stratégies de synthèse envisagées et les résultats obtenus sont détaillés

Linear and nonlinear optical properties of a quadrupolar carbo-benzene and its benzenic parent: The carbo-merization effect

International audienceHerein, the optical properties of thiophene-functionalized quadrupolar carbo-benzenes and a benzenic parent, of generic structure Th–Ctriple bondC–[core]–Ctriple bondC–Th, Th = R2C4HS, are comparatively investigated. Beyond the previously unknown dioctylthienylethynylbenzene (core = p-C6H4, R = nOct), two bis-dialkylthienylethynyl-carbo-benzenes (core = C18Ph4, R = nOct, nBu) are envisaged for the unique "carbo-aromatic" character of the C18 macrocycle. The three targets were synthesized from the corresponding ethynylthiophenes in 47, 20 and 10% yield, respectively, then characterized by classical methods such as NMR spectroscopy, and X-ray crystallography for one of the carbo-benzenes. Regarding linear and nonlinear optical properties, our results show that the carbo-merization induces a significant shift to lower energies of the one-photon electronic excitations accompanied by an 8-fold increase of the molar extinction coefficient compared to the parent molecule. Intriguingly, these excitations lead to a broad band of photoluminescence comprising decay transitions of the type S1 → S0 but also of the type S2 → S0. This phenomenon of emission from higher excited states, which is contrary to Kasha's rule, is assigned to - or revealed by - a reduction of the internal conversion efficiency between S2 and S1. Two-photon induced transitions are also enhanced, the two-photon absorption cross-section (σ2PA) being in average five times larger for the carbo-benzenes than for their benzene parent in the wavelength range 650–950 nm, with a maximum of σ2PA = 1430 GM (1 GM = 10−50 cm4 s/photon). Beyond a moderate nonlinearity, this comparative study provides quantitative insights about the way carbo-merization or insertion of a π-conjugated macrocycle between chromophoric functions (here thiophene rings) can tune optical properties of organic molecules. The optical properties of the bis-dialkylthienylethynyl-carbo-benzenes are also discussed in regard of recent reports on organic chromophores based on other types of π-conjugated macrocyclic cores

Linear and nonlinear optical properties of a quadrupolar carbo-benzene and its benzenic parent: The carbo-merization effect

International audienceHerein, the optical properties of thiophene-functionalized quadrupolar carbo-benzenes and a benzenic parent, of generic structure Th–Ctriple bondC–[core]–Ctriple bondC–Th, Th = R2C4HS, are comparatively investigated. Beyond the previously unknown dioctylthienylethynylbenzene (core = p-C6H4, R = nOct), two bis-dialkylthienylethynyl-carbo-benzenes (core = C18Ph4, R = nOct, nBu) are envisaged for the unique "carbo-aromatic" character of the C18 macrocycle. The three targets were synthesized from the corresponding ethynylthiophenes in 47, 20 and 10% yield, respectively, then characterized by classical methods such as NMR spectroscopy, and X-ray crystallography for one of the carbo-benzenes. Regarding linear and nonlinear optical properties, our results show that the carbo-merization induces a significant shift to lower energies of the one-photon electronic excitations accompanied by an 8-fold increase of the molar extinction coefficient compared to the parent molecule. Intriguingly, these excitations lead to a broad band of photoluminescence comprising decay transitions of the type S1 → S0 but also of the type S2 → S0. This phenomenon of emission from higher excited states, which is contrary to Kasha's rule, is assigned to - or revealed by - a reduction of the internal conversion efficiency between S2 and S1. Two-photon induced transitions are also enhanced, the two-photon absorption cross-section (σ2PA) being in average five times larger for the carbo-benzenes than for their benzene parent in the wavelength range 650–950 nm, with a maximum of σ2PA = 1430 GM (1 GM = 10−50 cm4 s/photon). Beyond a moderate nonlinearity, this comparative study provides quantitative insights about the way carbo-merization or insertion of a π-conjugated macrocycle between chromophoric functions (here thiophene rings) can tune optical properties of organic molecules. The optical properties of the bis-dialkylthienylethynyl-carbo-benzenes are also discussed in regard of recent reports on organic chromophores based on other types of π-conjugated macrocyclic cores

Expanding the carbo ‐Benzene Chemical Space for Electron‐Accepting Ability: Trifluorotolyl/Tertiobutyl Substitution Balance

International audienceWith the view to altering the lipophilicity and electron accepting ability of the tetraphenyl-carbo-benzene scaffold, peripheral fluorination of the C18 ring through aromatic linkers was envisaged from the C18Ph6 and o-tBu2C18Ph4 references, by replacement of two Ph substituents with two p-CF3-C6H4 counterparts (FTol). The synthesis relied on a [8+10] macrocyclization involving a common bis(trifluorotolyl)-tetraynedione, followed by reductive aromatization of the resulting [6]pericyclynediols. While p-FTol2C18Ph4 proved to be hardly tractable due to an extremely low solubility, p-FTol2-o-tBu2C18Ph2 could be extensively studied by X-ray crystallography, NMR and UV/Vis spectroscopy, voltammetry, STM imaging of monolayers, and AFM imaging of binary films with P3HT or PC71BM fabricated by spin-coating for organic photovoltaic cells and J−V curve measurement thereof. The electronic and polarity properties are correlated with moderate but consistent electron-withdrawing effects of the CF3 groups, in agreement with the DFT-calculated frontier orbitals and multipole moments. The results provide guidelines for optimization of fluorinated carbo-benzene targets

Linear and nonlinear optical properties of a quadrupolar carbo-benzene and its benzenic parent: The carbo-merization effect

International audienceHerein, the optical properties of thiophene-functionalized quadrupolar carbo-benzenes and a benzenic parent, of generic structure Th–Ctriple bondC–[core]–Ctriple bondC–Th, Th = R2C4HS, are comparatively investigated. Beyond the previously unknown dioctylthienylethynylbenzene (core = p-C6H4, R = nOct), two bis-dialkylthienylethynyl-carbo-benzenes (core = C18Ph4, R = nOct, nBu) are envisaged for the unique "carbo-aromatic" character of the C18 macrocycle. The three targets were synthesized from the corresponding ethynylthiophenes in 47, 20 and 10% yield, respectively, then characterized by classical methods such as NMR spectroscopy, and X-ray crystallography for one of the carbo-benzenes. Regarding linear and nonlinear optical properties, our results show that the carbo-merization induces a significant shift to lower energies of the one-photon electronic excitations accompanied by an 8-fold increase of the molar extinction coefficient compared to the parent molecule. Intriguingly, these excitations lead to a broad band of photoluminescence comprising decay transitions of the type S1 → S0 but also of the type S2 → S0. This phenomenon of emission from higher excited states, which is contrary to Kasha's rule, is assigned to - or revealed by - a reduction of the internal conversion efficiency between S2 and S1. Two-photon induced transitions are also enhanced, the two-photon absorption cross-section (σ2PA) being in average five times larger for the carbo-benzenes than for their benzene parent in the wavelength range 650–950 nm, with a maximum of σ2PA = 1430 GM (1 GM = 10−50 cm4 s/photon). Beyond a moderate nonlinearity, this comparative study provides quantitative insights about the way carbo-merization or insertion of a π-conjugated macrocycle between chromophoric functions (here thiophene rings) can tune optical properties of organic molecules. The optical properties of the bis-dialkylthienylethynyl-carbo-benzenes are also discussed in regard of recent reports on organic chromophores based on other types of π-conjugated macrocyclic cores