Ce travail de thèse a permis de concevoir, synthétiser et caractériser de nouveaux verres moléculaires à base de carbazole pour la réalisation de cellules solaires DSSC solide ou de type pérovskite. Ces structures sont une alternative à la molécule de référence à base de spirobifluorène (Spiro-OMeTAD) utilisée majoritairement dans les dispositifs hybrides. Nous avons optimisé une voie de synthèse simple et rapide d’un « synthon carbazole » servant de précurseur à la conception d’une large variété de verres moléculaires transporteur de trous (HTM). Cette voie de synthèse a ainsi permis de réaliser une première génération de molécules possédant un unique synthon carbazole substitué par des groupements aryles (naphtalène, pyrène, triazatruxène) puis une seconde génération incorporant deux synthons carbazole séparés par un espaceur alkylé. Dans les deux cas, les voies de synthèse sont simples et les rendements de conversion d’énergie générés en DSSC solides sont prometteurs (entre 2,22 et 2,47 % avec le colorant D102). Une étude préliminaire de vieillissement consistant à analyser la dégradation en thermolyse et photolyse d’un film mince utilisant un HTM carbazole montre que ce dernier (Cz-P) possède une stabilité comparable au Spiro-OMeTAD en absence de dioxygène. Finalement, deux verres moléculaires ont été étudiés en cellules de type pérovskite permettant d’atteindre des rendement de conversion de 13,08 % et 12,41 % (pour Cz-P et Cz-PF) quasi-identiques à ceux à base de Spiro-OMeTAD (13,45 %) confirmant que ces structures à base de synthon carbazole sont aussi de bons candidats pour la réalisation de cellule pérovskite performantes. / The aim of this work was to design, synthesize and characterize new carbazole based molecular glasses for the realization of solid state DSSC or perovskite solar cells. These structures would be an alternative to the reference molecule based on spirobifluorene (Spiro-OMeTAD) mainly used in hybrid devices. We have optimized a simple way to synthetize a "synthon" as a precursor to the design of a wide variety of efficient hole transporting materials (HTM). This synthesis pathway has allowed producing a first generation of molecules based on a single carbazole synthon substituted by aryl groups (naphthalene, pyrene, triazatruxene) then a second generation incorporating two carbazole synthons separated by an alkyl spacer. In both cases, the synthesis pathways are simple and the energy conversion efficiencies generated in solid DSSCs are promising (between 2.22 % and 2.47 % with the D102 dye). A preliminary ageing study has consisted in analyzing the degradation during thermolysis or photolysis of a carbazole based thin film. It was shown that Cz-P possesses stability similar to Spiro-OMeTAD in the absence of oxygen. Finally, two carbazole molecular glasses were studied in perovskite cells to achieve conversion efficiencies of 13.08 % and 12.41 % (for Cz-P and Cz-PF respectively) almost identical to the one based on Spiro-OMeTAD (13.45 %), confirming that these carbazole based structures are good candidates for the realization of efficient perovskite cells.

Dans cette thèse sont développées les synthèses et caractérisations de nouveaux polymères conjugués pour des applications dans l’électronique organique. Ces polymères ont été synthétisés via des réactions de polymérisation sans utilisation de métaux de transition. Des polyazomethines à base de carbazole ont ainsi été synthétisés par polycondensation entre des carbazole portant des fonctions amine et aldéhyde en positions 2,7 et 3,6. Leurs propriétés optiques et électroniques ont été étudiées en fonction de la position des fonctions imines ainsi formées. Un comonomère de type EDOT a ensuite été intégré dans le polymère et l’impact de ce comonomère sur les propriétés du copolymère ainsi formé a été étudié.Des polymères à base d’acide squarique et croconique ont ensuite été synthétisés. En faisant varierles conditions de synthèse, les propriétés optoélectroniques ont pu être contrôlées, permettant d’obtenir des composés présentant une émission blanche, qui ont ensuite été intégrés en tant que couche active dans des dispositifs de type OLED.Enfin, des polymères plus originaux ont été étudiés, utilisant des réactions de polymérisation originale, permettant par exemple la formation de benzobisthiazole in situ. D’autres polymères ont été synthétisés en intégrant dans leur chaine des monomères originaux, comme la tetrazine ou la divanilline. Les propriétés optoélectroniques de ces composés ont ensuite été étudiées en vue deleur éventuelle intégration dans des dispositifs. / In this work, synthesis and characterizations of new conjugated polymers are described.These polymers, developed for their integration into devices, have been synthesized via transitionmetalfree polymerizations. Carbazole based polyazomethines have been synthesized via polycondensation reactions between di-substituted carbazoles, bearing amino and formyl functionsin positions 3,6 or 2,7. Optical and electronical properties of such polymers have been studieddepending of the linkage position. A comonomer EDOT has then been integrated into the polymer chain, and impact of such insertion has been studied. Squaric and croconic acid base polymers have also been synthesized. By varying polymerization conditions, optoelectronic properties have been tuned, leading to the formation of polymers exhibiting a white emission. These polymers have then been integrated into OLED, as the active layer. Finally, more original polymers have been synthesized, using more original reactions or monomers such as by forming in situ benzobisthiazole. Other polymers integrating more originals monomers, such a tetrazine or divanillin, have been synthesized. Optoelectronic properties of such materials have been studied for the purpose of their integration into devices.

Homopolymers and copolymers produced from aromatic based methacrylates, acrylates, and dimethacrylates are excellent materials with many applications in dentistry, microelectronics, and optics, including optical eye wear, fiber optics, and non-linear optics, such as holography. Carbazole based polymers have demonstrated good optical, photo-refractive, and charge-transporting properties, combined with ease of processing. The objective of this research was to design, synthesize, and characterize high refractive index polymers and copolymers for use in optical spectacle lenses of eyeglasses. Additionally, other interesting attributes were observed for selected carbazole based polymers, such as high thermal stability and birefringence, which could lend these materials to other uses, such as non-linear optics and electronic data storage. A family of novel, high refractive index homopolymers and copolymers were synthesized by incorporating carbazole, along with other aromatic substituents, into methacrylates, acrylates, and dimethacrylates. Subsequent free radical polymerizations provided for high refractive index materials well suited for lightweight optical spectacles and other applications. The refractive index of materials can be increased by increasing the polarizability of substituent groups. By incorporating oxygen, sulfur, or sulfoxide groups into polymers, high refractive index polymers have been attained. By reacting the phenol, aromatic diols, or aromatic thiols with 9-(2,3-epoxypropyl)-carbazole, the refractive index of the final polymer can be increased further. The reaction of the carbazole based intermediate with methacryloyl chloride or methacrylic anhydride eliminated any hydroxyl groups in the final methacrylate or dimethacrylate. Hydroxyl groups undergo intermolecular hydrogen bonding, which increases viscosity. The absence of hydrogen bonding in the final methacrylated monomers reduces viscosity, which is desirable for processing. Novel carbazole based monomers and polymers were characterized in terms of molecular composition and molecular weight, thermal properties, such as melting point, glass transition temperature, and decomposition, and in terms of optical properties, such as refractive index. The AIBN initiated carbazole-phenoxy based methacrylate polymerization was followed using in-situ FTIR, which showed the reaction to be completed within 40 minutes in DMAC at 90°C. Photo-DSC was used to determine the heat of polymerization (DHp) for the carbazole-phenoxy based methacrylate, which was found to be -39.4 kJ/mole. One and two dimensional 1H NMR was used to characterize the molecular structure of the carbazole-phenoxy based methacrylate monomer. The carbazole-phenoxy based methacrylate homopolymer had a surprisingly high decomposition temperature. 13C NMR spectroscopy experiments and molecular modeling were employed to explore the configuration of the polymerized carbazole-phenoxy based methacrylate. The lack of head-to-head linkages due to steric considerations could explain the higher thermal stability observed for the carbazole-phenoxy based methacrylate polymer. Refractive indices of these carbazole based methacrylates, acrylates, and dimethacrylate polymers ranged from 1.53 to 1.63. Statistical copolymers of carbazole based methacrylates with methyl methacrylate were also produced by solution polymerization in DMAC, and characterized. Using free radical polymerization techniques, homopolymers and copolymers of the carbazole functionalized methacrylates, acrylates, and dimethacrylates were readily obtained. This research demonstrated a variety of carbazole based chemistries which could produce controlled linear and cross-linked materials with high refractive index values and other interesting features. / Ph. D.

Within this thesis the first total syntheses of eight biologically active natural products from the family of carbazole alkaloids, antiostatins A1 to A4 and B2 to B5, were established. Spectroscopic data of the synthesised natural products are in good agreement with the isolated antiostatins from Streptomyces cyaneus 2007-SV1, which confirms the molecular structures assigned to the natural products. The total synthesis of the antiostatins A1 to A4 and B2 to B5 were achieved employing the iron-mediated synthesis to form the carbazole nucleus from a cyclohexadienylium iron salt and appropriate arylamines. This transition metal-mediated approach could be applied to all antiostatins in excellent yields. The antiostatins A1-4 and B2-5 represent the first carbazole alkaloids with an acetamide or substituted biuret chain. Introduction of the sophisticated substituents proceeded selectively on C-4 in high yields. Antiostatins A1 to A4 and B2 to B5 could be synthesised over eight steps from a tricarbonyliron-coordinated cyclohexadienylium salt. The overall yields are in the range of 31 – 63%.

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Mémoire numérisé par la Direction des bibliothèques de l'Université de Montréal.

N-phenylpyridin-2-amine , treated with stochiometric amount of palladium(II) acetate in dichloromethane at 65-70¢J for 4 h, to give high yield palladacycle 53. The reaction of palladacycle 53 with potassium aryltrifluoroborates in 1,4-dioxane at 140¢J for 24 h, could give a variety of N-(2-pyridinyl)carbazoles 55a-55m via sequential C-H bond activation. Carbazole derivative 55a reacted with irdium chloride gave iridium dimer, which followed by addition of picolinic acid via ligand exchange will form iridium complexes, which can further be utilized as OLEDs materials.

Since the discovery of the photovoltaic effect in bulk heterojunction devices¡Mthe considerable publications in PSCs have been reported¡OPSCs based on the concept of bulk heterojunction (BHJ) configuration where active layer comprises of a p-type donor (conjugated polymer) and a n-type acceptor (fullerene derivative) materials¡Mrepresents the most useful strategy to maximize the internal donor-acceptor interface area allowing for efficient charge separation¡OTo further enhance the power conversion efficiency from solar cells made of poly(3-hexylthiophene)/[6,6]-phenyl C61 butyric acid methyl ester (P3HT/PCBM) ¡M a new conducting polymer with optimized band energy levels are demonstrated to be one of the key properties¡OIn this study¡MI synthesized a soluble and strongly visible-light absorbing alternating conducting polymer using Suzuki coupling polymerization method¡OThe UV-Vis absorption spectra of copolymer contains an intramolecular charge transfer (ICT) transition band¡Mwhich leads to absorption extending to near-infrared region and optical band gaps is 1.55 eV¡OThe photo-electron spectroscopy in air(PESA) measurements show that the HOMO level of the polymer is ~5.0eV which is lower than P3HT¡O

A one-pot synthesis of ortho-arylated 9-(pyridin-2-yl)-9H-carbazoles via C-H bond activation, in which palladium(II)-catalyzed cross-coupling of 9-(pyridin-2-yl)-9H-carbazoles with potassium aryltrifluoroborates is presented. Silver nitrate and tert-butanol were proved to be the best oxidant and solvent for the process, respectively. The product yields fluctuated from modest to excellent, and the reaction showed sufficient functional group tolerance. p-Benzoquinone served as an important ligand for the transmetalation and reductive elimination steps in the catalytic process. The key intermediate of the reaction, 9-(pyridin-2-yl)-9H-carbazole palladacycle was isolated and confirmed by X-ray crystallography. The kinetic isotope effect (kH/kD) for the C-H bond activation step was measured as 0.87. In addition, Hammett experiment gave a negative rho value, -2.14 with a reasonable correlation (R2 = 0.90). The directing group, pyridyl was demonstrated as a removable functional group. Finally, a rational catalytic mechanism is presented based on all experimental evidence.

In this thesis, a novel blue Poly (arylene ether) s polymer was prepared for the organic polymer light emitting diodes which was composed of the main material anthracene difluoro monomer derivatives, and object material of triphenylamine with the extension structure similar to the literature seen BD-1 asymmetric derivatives, as the hole transport material of carbazole of the diol derivatives. In general, Anthracene derivatives and BD-1, often seen in the literature as the host, guest blue polymer doping, the main use to Forster energy transfer to transfer energy to the guest, so it has good luminous efficiency. Anthracene, flat Good, easy to crystallization during evaporation, resulting in leakage generated; and the deposition of the multilayer structure will hinder charge injection to the emitting layer. From the angle of the molecular design of this study. (1) Use of the CF bond and Carbazole increase the steric hindrance of the polymer chain and change by fluoride compounds of the highest occupied molecular orbital - lowest unoccupied molecular orbital energy level. (2) The hole transport layer to import into the emitting layer. The two monomers Anthracene derivatives fluoride monomer the Carbazole of diol derivatives via nucleophilic polycondensation synthesis of a novel in proper proportion, Blue polymer. Component parts, the Blue poly aromatic ether polymer doped with a small amount of blue light-emitting guest as a component layer of the component structure: ITO / PEDOT: PSS / emitting layer / LiF / Al light-emitting layer can make use of spin coating of solvent process, and its advantage is the convenience of the process and a large area. The undoped guest before the Blue polymer production the PLED starting voltage can be reduced to 4.5 V, and maximum brightness 7 466 cd/m2, efficiency as high as 4.2 cd / A. C.I.E. coordinates of (0.15,0.08), very close to the official regulations of the NTSC Blue coordinates (0.14,0.08). When doped with 3% of the guest, the starting voltage can be reduced to 4.5 V, maximum brightness of 12104 cd/m2 and efficiency as high as 5.79 cd/A.