Este trabalho tem como principais objetivos: desenvolver procedimentos sintéticos e novos materiais poliméricos que apresentem boa condutividade elétrica, estudar o comportamento eletro-óptico dos polímeros obtidos, desenvolver procedimentos para a construção de dispositivos eletroluminescentes, caracterizá-los e correlacionar as características eletro-ópticas observadas com a constituição da camada ativa polimérica. Foram realizadas diversas sínteses objetivando a preparação de polifluorenos com diferentes estruturas químicas a partir de monômeros difuncionais aromáticos boronados e bromados, utilizando uma mesma rota de acoplamento de Suzuki. Assim, foram preparados três polímeros, poli[2,7-(9,9-dioctilfluoreno)] (PF, polifluoreno), poli[1,4-fenileno-alt-2,7- (9,9-dioctilfluoreno)] [PFP, poli(fluoreno-fenileno)] e poli[(1,4-fenileno-2-flúor)-alt-2,7-(9,9- dioctilfluoreno)] [PFPF, poli(fluoreno-fenileno)fluorado]. Para obtenção destes polifluorenos com bom rendimento e com pureza adequada para a preparação de dispositivos poliméricos eletroluminescentes, foi necessário testar diversas condições de reação, até a otimização de um procedimento sintético robusto. Os polifluorenos preparados foram exaustivamente purificados por extração e solubilização-precipitação. Todos os polifluorenos tiveram a sua estrutura e composição químicas caracterizadas e confirmadas pelas técnicas de espectroscopia no infravermelho (FTIR), espectroscopia de ressonância magnética nuclear de hidrogênio (¹HNMR) e espectroscopia de energia dispersiva de raios-X (EDX). As massas molares médias e a polidispersão foram determinadas por cromatografia de permeação em gel (GPC). Soluções em clorofórmio dos polifluorenos foram analisadas por espectroscopias de absorção e emissão no UV-Vis. Estes resultados nos forneceram informações importantes quanto às propriedades de fotoluminescência dos polifluorenos obtidos. Até o momento, sabe-se que todos os três polímeros emitem cor azul e dentre as três estruturas estudadas, o PFPF apresentou maior intensidade de fluorescência. Para a fabricação dos P-OLEDs (Diodos Orgânico-Polimérico Emissor de Luz) foram feitas soluções de clorofórmio em concentrações de 1% dos três tipos de polímeros. Também foi estudada a influência dos compostos ETL (electron transport layer) (Alq3 ou butyl-PBD) com concentrações de 0,5%. Quando aplicada uma tensão no dispositivo, o PFPF apresentou menor tensão de operação entre os polímeros estudados. A partir das curvas de tensão vs. corrente, verificou-se que a adição do butyl-PBD nos três tipos de polímeros diminui a tensão de limiar em comparação com os dispositivos sem composto ETL. Os comprimentos de onda de eletroluminescência dos dispositivos polarizados permaneceram constante mesmo com a adição dos dois compostos ETL (Alq3 ou butyl-PBD). / This work has as main objectives: develop synthetic procedures and new electroluminescent polymeric materials that have good electrical conductivity, study the behavior of polymer systems thus obtained, and develop procedures for the construction of electroluminescent devices, characterize them and correlate the photo- electrical behavior with the features of the constitutive active polymeric layer Several syntheses were performed aiming at preparing polyfluorenes with different structures from boronated and brominated difunctional aromatic monomers using a Suzuki coupling route. So far, three polymers were prepared, poly[2,7-(9,9-dioctylfluorene)] (PF, polyfluorene), poly[1,4-phenylene-alt-2,7-(9,9-dioctylfluorene)] [PFP, poly(fluorenephenylene)] and poly[1,4-phenylene-2-fluoro)-alt-2,7-(9,9-dioctylfluorene)] [PFPF, fluorinated poly(fluorene-phenylene)]. To obtain these polyfluorenos with good yield and purity suitable for preparing polymeric electroluminescent devices, it was necessary to test various reaction conditions and to optimize a robust synthetic procedure. The polyfluorenes prepared were thoroughly purified by extraction and solubilization-precipitation. All polyfluorenes have had their structures and chemical composition characterized and confirmed by infrared spectroscopy (FTIR), and hydrogen and carbon-13 nuclear magnetic resonance spectroscopy (¹HNMR and 13CNMR). The average molar masses and polydispersity were determined by gel permeation chromatography (GPC). Polyfluorenes in chloroform solutions were analyzed by the UV-Vis absorption and emission spectroscopy. These results provided us with important information regarding the photoluminescence properties of polyfluorenes thus obtained. Until now, it is known that all three polymers emit in the blue region and among the three structures, the PFPF has the highest fluorescence intensity. The construction of PLEDs was carried out from the chloroform solutions at concentrations of 1% for each of the all three types of polymers. The influence of an ETL (electron transport layer) compound (Alq3, PBD) was also studied, and its concentration was kept constant at 5% in the polymer solution. Tests of the devices under applied voltage have shown a higher stability for PFPF among all. From the voltage vs. current curves, it was possible to observe that the addition of PBD decreased the threshold voltage for the devices prepared from the three types of polymers. The wavelength of electroluminescence remained constant despite the addition of the ETL compound (Alq3 or butyl-PBD).

Die vorgelegte Arbeit befasst sich mit der Untersuchung von Zusammenhängen zwischen der Struktur dünner organischer Schichten und stellt einen Bezug zur Leitfähigkeit der Schichten her. Sie liefert einen Beitrag zum vertieften Verständnis der Transporteigenschaf-ten organischer Halbleiter und soll so zur Verbesserung organischer elektronischer Bauele-mente beitragen. Es ist bekannt, dass die Effizienz von Organischen Leuchtdioden (OLEDs) stark von der Qualität der eingesetzten dünnen Filme abhängt. Es ist deshalb interessant, die Strukturen technologisch interessanter organischer Filme mittels Scanning Probe Mikrosko-pie (SPM) zu charakterisieren, um ein besseres Verständnis sowohl der Oberflächen-Morphologie als auch der molekularen/atomaren Packungen zu erhalten. <br><br> Die Untersuchung von Quaterthiophen (4T), welches vielfach in Feldeffekt-Transistoren eingesetzt wird, bildet einen ersten Schwerpunkt der Arbeit. Es konnte eine neue Kristall-struktur von 4T gefunden werden, die bisher nicht bekannt war. Dafür wurden Quaterthi-ophen-Filme untersucht, welche auf Kaliumphthalat (KAP) aufwuchsen. Die Aufklärung der neuen Struktur gelang durch Kombinierten Einsatz von optischen und Röntgen-Beugungsmessungen. Zur Bestätigung der triklinen Kristall-Einheitszelle mit den Parame-tern a = 0,721 nm, b = 0,632 nm, c = 0,956 nm und α = 91o, β = 91,4o, γ = 91o wurde außer-dem die Atomkraft-Mikroskopie (AFM) angewendet. <br><br> In Fortführung der rastermikroskopischen Messungen sind die Morphologien von Filmen vier weiterer organischer Materialien technologischer Relevanz untersucht worden: He-xanthiol-Monoschichten auf Gold, Azobenzenthiol-Monoschichten auf Gold, Para-Phenylenvinylen-Oligomer-Filme auf Gold und Phenyl-Oxadiazol-Filme auf Gold. Dafür kam zusätzlich die Ultrahochvakuum-Scanning-Tunneling-Mikroskopie (UHV-STM) zum Einsatz. Es zeigte sich eine Vielzahl morphologischer Eigenheiten, deren Besonderheiten sowohl von den gewählten Substraten als auch von der chemischen Struktur der untersuchten organischen Materialien abhängen. So zeigen Para-Phenylenvinylen-Oligomer-Filme eine Stäbchen- und Oxadiazol-Filme eine Körnchen-Struktur auf Gold. <br><br> Auf Basis dieser Kenntnisse gelang es, das optisch induzierte Schalten von Azobenzen durch STM-Untersuchungen und durch Scanning Tunneling Spektroskopie (STS) auf molekularer Skale nachzuweisen. <br><br> Die Topographie einer Reihe von Poly(3,4-ethylendioxythiophen)-(PEDOT)-Filmen und de-ren Bezug zu den Ladungstransporteigenschaften dieser Filme war ein weiterer Arbeits-schwerpunkt. PEDOT-Filme auf Indium-Zinn-Oxid (ITO) kommen in organischen elektro-nischen Bauelementen als Lochinjektionsschichten zum Einsatz. Für die Schichtherstellung kamen Dispersionen des Polymers unterschiedlicher Konzentration zur Anwendung: Mittels AFM und STM konnte gezeigt werden, dass unterschiedliche Konzentrationen zu unter-schiedlichen Topographien führen. Besonders die Oberfläche der Filme mit hoher Konzent-ration von PEDOT, d.h. die der leitfähigsten Filme, wird durch eine körnchenartige Struktur eingebetteter Teilchen charakterisiert. Durch STM Strom-Abstands-(I-d)-Untersuchungen wurde gefunden, dass diese Teilchen die „Spitze eines Eisbergs“ leitfähiger Domänen dar-stellen. Ausgehend von dieser Erkenntnis wird ein Strukturmodell für die Filme vorgeschla-gen, in dem die leitfähigen Domänen / Partikel in eine weniger leitfähige Matrix eingebettet sind. Durch Zugabe von Polyolen wie Sorbitol zur PEDOT-Dispersion ließen sich Filme mit höherer Leitfähigkeit herstellen. Eine klare Abhängigkeit zwischen der Leitfähigkeit und der bisher nicht beschrieben nano-Morphologie wurde gefunden. / It is known that the efficiency of organic light-emitting devices (OLEDs) is strongly influenced by the ’quality′ of the thin films [1]. On the basis of this conviction, the work presented in this thesis aimed to obtain a better understanding of the structure of organic thin films of general interest in the field of organic light emitting devices by using scanning probe microscopies (SPMs). <br><br> A not yet reported crystal structure of quaterthiophene film grown on potassium hydrogen (KHP) is determined by optical measurements, a simulation program, diffraction at both normal incidence and grazing angle and AFM. The crystal cell is triclinic with parameters a = 0.721 nm, b = 0.632 nm, c = 0.956 nm and a = 91°, b = 91.4°, g = 91° [2]. <br><br> The morphologies of four organic thin films deposited on gold are characterized by ultra high vacuum scanning tunneling microscopy (UHV-STM). Terraces in an hexanethiol monolayer, lamellar structures in an azobenzenethiol monolayer, rods in a a poly(paraphenylenevinylene) oligomer film and a granular morphology in an oxadiazole film are shown. <br><br> The topographies of a series of poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate) (PEDOT/PSS) films deposited on indium-tin oxide (ITO) and gold obtained from dispersions with PEDOT:PSS weight ratios of 1:20, 1:6 and 1:1 are investigated by AFM. It is demonstrated that the films show the same topography on gold and on ITO. It is shown that the PEDOT films eliminate the spike features of ITO. It is reported that PEDOT 1:20 and 1:6 appear indistinguishable between each other but different from PEDOT 1:1 (the most conductive). <br><br> Coupling STM and I-d measurements, a not yet reported structural model of PEDOT 1:1 on gold is obtained [3]. In this model the surface presents grains and the bulk particles/domains rich in PEDOT embedded in a PEDOT-poor matrix. The equation of conductivity is derived. <br><br> A STM investigation of four PEDOT films deposited on ITO obtained from dispersions with the same PEDOT:PSS weight ratio of 1:1 is carried out [4]. The films differ either for the presence of sorbitol or for a different synthetic route (and they present different conductivities). For the first time a quantitative and qualitative correlation between the nanometer-scale morphology of PEDOT films with and without sorbitol and their conductivity is established.

Depuis quelques années, un essor important est observé pour les diodes électroluminescentes organiques (OLEDs) se traduisant par une intégration progressive dans de nombreux appareils électroniques destinés au grand public : smartphones, tablettes tactiles, téléviseurs, … Cependant, malgré de nombreux avantages, la haute sensibilité des empilements organiques à l'atmosphère ambiante, et l'observation de dégradations à la surface des dispositifs, sont les causes principales limitant l'utilisation massive de cette technologie. L'encapsulation des dispositifs à l'aide d'empilements barrières est susceptible de résoudre tout ou en partie ces problèmes, L'objectif de cette thèse est de développer et de caractériser de nouveaux empilements multicouches inorganique-organique barrières à l'humidité et à l'oxygène, afin de maintenir les performances des OLEDs le plus longtemps possibles. Des solutions d'encapsulations couches minces, réalisées directement à la surface des dispositifs, ont été développées et évaluées sur OLEDs. Les empilements sont composés d'une alternance entre un film d'oxyde d'aluminium déposé par ALD (Atomic Layer Deposition) et une couche de résine organique. Les empilements OLEDs utilisés étant fragiles, les dépôts ont été effectués dans des conditions douces, notamment à basse température (T < 100 °C). Parallèlement, une méthode de caractérisation des propriétés barrières a été mise en place, afin d'évaluer les performances intrinsèques des différentes couches ou empilements d'encapsulation utilisés, et apporter une compréhension sur le mécanisme de protection. / Over the last few years, a significant growth is observed for OLEDs (Organic Light-Emitting Diodes) resulting in the gradual integration into many electronic devices for mass-market applications: smartphones, touchscreen tablet, TV … However, despite many advantages, the high sensitivity of the organic stacks in ambient atmosphere, and the surface degradation of the devices, are the main causes limiting the massive use of this technology. The encapsulation of the devices thanks to barrier multilayers can solve some or all these problems. The aim of this thesis is to develop and to characterize new inorganic-organic multilayers as a barrier against moisture and oxygen, in order to preserve OLEDs performances. Solutions for the thin layer encapsulation, made directly in the surface of the devices, have been developed and evaluated on OLEDs. The encapsulation stacks are based on alternating between a film of aluminum oxide deposited by ALD (Atomic Layer Deposition) and a layer of organic resin. Stacks of OLEDs are fragile, and the deposits have been carried out under mild conditions, especially when temperatures are low (T < 100 °C). A the same time, a method for the characterization of the barrier properties has been carried out, in order to evaluate the intrinsic performances of thin films or encapsulation stacks used, and to provide an understanding of the protection mechanism.

Este trabalho tem como principais objetivos: desenvolver procedimentos sintéticos e novos materiais poliméricos que apresentem boa condutividade elétrica, estudar o comportamento eletro-óptico dos polímeros obtidos, desenvolver procedimentos para a construção de dispositivos eletroluminescentes, caracterizá-los e correlacionar as características eletro-ópticas observadas com a constituição da camada ativa polimérica. Foram realizadas diversas sínteses objetivando a preparação de polifluorenos com diferentes estruturas químicas a partir de monômeros difuncionais aromáticos boronados e bromados, utilizando uma mesma rota de acoplamento de Suzuki. Assim, foram preparados três polímeros, poli[2,7-(9,9-dioctilfluoreno)] (PF, polifluoreno), poli[1,4-fenileno-alt-2,7- (9,9-dioctilfluoreno)] [PFP, poli(fluoreno-fenileno)] e poli[(1,4-fenileno-2-flúor)-alt-2,7-(9,9- dioctilfluoreno)] [PFPF, poli(fluoreno-fenileno)fluorado]. Para obtenção destes polifluorenos com bom rendimento e com pureza adequada para a preparação de dispositivos poliméricos eletroluminescentes, foi necessário testar diversas condições de reação, até a otimização de um procedimento sintético robusto. Os polifluorenos preparados foram exaustivamente purificados por extração e solubilização-precipitação. Todos os polifluorenos tiveram a sua estrutura e composição químicas caracterizadas e confirmadas pelas técnicas de espectroscopia no infravermelho (FTIR), espectroscopia de ressonância magnética nuclear de hidrogênio (¹HNMR) e espectroscopia de energia dispersiva de raios-X (EDX). As massas molares médias e a polidispersão foram determinadas por cromatografia de permeação em gel (GPC). Soluções em clorofórmio dos polifluorenos foram analisadas por espectroscopias de absorção e emissão no UV-Vis. Estes resultados nos forneceram informações importantes quanto às propriedades de fotoluminescência dos polifluorenos obtidos. Até o momento, sabe-se que todos os três polímeros emitem cor azul e dentre as três estruturas estudadas, o PFPF apresentou maior intensidade de fluorescência. Para a fabricação dos P-OLEDs (Diodos Orgânico-Polimérico Emissor de Luz) foram feitas soluções de clorofórmio em concentrações de 1% dos três tipos de polímeros. Também foi estudada a influência dos compostos ETL (electron transport layer) (Alq3 ou butyl-PBD) com concentrações de 0,5%. Quando aplicada uma tensão no dispositivo, o PFPF apresentou menor tensão de operação entre os polímeros estudados. A partir das curvas de tensão vs. corrente, verificou-se que a adição do butyl-PBD nos três tipos de polímeros diminui a tensão de limiar em comparação com os dispositivos sem composto ETL. Os comprimentos de onda de eletroluminescência dos dispositivos polarizados permaneceram constante mesmo com a adição dos dois compostos ETL (Alq3 ou butyl-PBD). / This work has as main objectives: develop synthetic procedures and new electroluminescent polymeric materials that have good electrical conductivity, study the behavior of polymer systems thus obtained, and develop procedures for the construction of electroluminescent devices, characterize them and correlate the photo- electrical behavior with the features of the constitutive active polymeric layer Several syntheses were performed aiming at preparing polyfluorenes with different structures from boronated and brominated difunctional aromatic monomers using a Suzuki coupling route. So far, three polymers were prepared, poly[2,7-(9,9-dioctylfluorene)] (PF, polyfluorene), poly[1,4-phenylene-alt-2,7-(9,9-dioctylfluorene)] [PFP, poly(fluorenephenylene)] and poly[1,4-phenylene-2-fluoro)-alt-2,7-(9,9-dioctylfluorene)] [PFPF, fluorinated poly(fluorene-phenylene)]. To obtain these polyfluorenos with good yield and purity suitable for preparing polymeric electroluminescent devices, it was necessary to test various reaction conditions and to optimize a robust synthetic procedure. The polyfluorenes prepared were thoroughly purified by extraction and solubilization-precipitation. All polyfluorenes have had their structures and chemical composition characterized and confirmed by infrared spectroscopy (FTIR), and hydrogen and carbon-13 nuclear magnetic resonance spectroscopy (¹HNMR and 13CNMR). The average molar masses and polydispersity were determined by gel permeation chromatography (GPC). Polyfluorenes in chloroform solutions were analyzed by the UV-Vis absorption and emission spectroscopy. These results provided us with important information regarding the photoluminescence properties of polyfluorenes thus obtained. Until now, it is known that all three polymers emit in the blue region and among the three structures, the PFPF has the highest fluorescence intensity. The construction of PLEDs was carried out from the chloroform solutions at concentrations of 1% for each of the all three types of polymers. The influence of an ETL (electron transport layer) compound (Alq3, PBD) was also studied, and its concentration was kept constant at 5% in the polymer solution. Tests of the devices under applied voltage have shown a higher stability for PFPF among all. From the voltage vs. current curves, it was possible to observe that the addition of PBD decreased the threshold voltage for the devices prepared from the three types of polymers. The wavelength of electroluminescence remained constant despite the addition of the ETL compound (Alq3 or butyl-PBD).

[pt] A partir da associação de condensações aldólicas e acoplamentos cruzados em blocos de construção arilcarbonílicos já conhecidos, é possível modular as estruturas conjugadas dos produtos, direcionando-os a diferentes aplicações. Sendo assim, na presente tese, buscou-se realizar a síntese de todos os compostos por meio de associações de condensações aldólicas e acoplamentos. Este trabalho está dividido em quatro capítulos que dizem respeito a: (i) síntese e avaliação fotofísica de híbridos de chalconas e benzotiadiazolas (BTDs); (ii) síntese e aplicação de híbridos BTD-chalconas como dispositivos OLEDs; (iii) síntese de chalconas e BTDs e avaliação de potenciais fotossensibilizadores para DSSCs (células solares sensibilizadas por corante); (iv) síntese de beta-arilchalconas com potencial atividade antiestrogênica. Levando em consideração as reconhecidas propriedades fotofísicas de chalconas e derivados de BTDs, é descrita a síntese de novos híbridos BTDchalcona fotoativos. Os produtos foram obtidos em rotas de duas etapas (reação de Suzuki e posterior condensação aldólica) com rendimentos reacionais variando entre 32 e 64 por cento. As modulações nas estruturas foram realizadas de tal forma que os compostos fossem emissivos no estado agregado. Sabendo das limitações do desenvolvimento de filmes luminescentes relacionadas ao efeito de quenching causado por agregação (ACQ), buscou-se sintetizar compostos com propriedades do tipo AIEE (emissão aumentada induzida por agregação). Os estudos de suas propriedades fotofísicas demonstraram que o composto com arquitetura arilóxiBTD-chalcona apresentou os melhores resultados nos quais foram observados aumentos expressivos na intensidade de fluorescência (30x) e no rendimento quântico de fluorescência (de 0,0070 a 0,143) em estado agregado. Com estes dados, novos análogos foram sintetizados respeitando o esqueleto do tipo arilóxiBTD-chalcona (ou -fluoreno) com rendimentos que variaram de 42 a 79 por cento. Os novos análogos também apresentaram AIEE e foram aplicados como camadas emissoras em OLEDs de estrutura bicamada para avaliação e comparação dos seus desempenhos eletroluminescentes. A associação de acoplamento cruzado e condensação aldólica também foi utilizada como estratégia para a produção de novos fotossensibilizadores para DSSCs. Para tal, buscou-se sintetizar compostos do tipo D-pi-A-pi-A, nos quais os grupos aceptores terminais têm a função de ancoradores de TiO2. O uso deste tipo de estrutura facilita a injeção de elétrons devido à transferência direcional de elétrons do doador para a porção aceptora. Com base nisso, foram sintetizados novos derivados de chalconas e BTDs. As sínteses foram realizadas em duas etapas resultado em rendimentos de 35 a 44 por cento. Estudos eletroquímicos apontaram bons valores de HOMO, LUMO e band gap para todos os compostos. Os valores de LUMO se mostraram acima da faixa de condução do semicondutor TiO2 (-4,0 eV), garantindo a força motriz necessária para o direcionamento dos elétrons. Além disso, os valores de HOMO de todos os compostos se mostraram inferiores ao potencial redox do eletrólito (-4,8 eV) gerando uma alta força motriz para regeneração do corante. Por meio de Espectrometria de UV-Vis, foi observado que os compostos absorvem em região próxima a 350 nm em diferentes solventes, o que dificulta o uso destes como DSSCs. Por fim, no último capítulo foi apresentada uma nova estratégia para a obtenção de moléculas potencialmente bioativas a partir da associação entre condensações aldólicas e reações de acoplamento. O sistema alfa-beta insaturado da chalcona torna essa uma interessante plataforma para inserção régio- e estereosseletiva de substituintes arílicos na porção olefínica do substrato. A partir de uma estratégia de inserção de porções arílicas já descrita por nosso grupo, aplicamos estas para a síntese de análogos do tamoxifeno, fármaco utilizado atualmente no tratamento de alguns tumores de mama. Seis produtos foram sintetizados por meio de uma reação de Heck, resultando em misturas E/Z de aproximadamente 50:50 e rendimentos de 29 a 57 por cento. / [en] It is possible to modulate the conjugated structures of the products, directing them to different applications from the association of aldol condensations and crosscouplings in known arylcarbonyl building blocks,. In this sense, this thesis is divided into four chapters concerning: (i) synthesis of analogues and hybrids of chalcones and BTDs; (ii) synthesis and application of chalcone-BTD hybrids as OLED devices; (iii) synthesis and evaluation of potential photosensitizers for DSSCs (dye-sensitized solar cells); (iv) synthesis of compounds with potential antiestrogenic activity. For the synthesis of all compounds, associations of aldol condensations and cross couplings were performed. Considering the recognized photophysical properties of chalcones and BTD derivatives, the synthesis of new photoactive BTD-chalcone hybrids is described. The products were obtained in two-step routes (Suzuki reaction and aldol condensation) and reaction yields ranged from 32 to 64 percent. The modulations in the structures were performed in such a way that the compounds were emissive in the aggregated state. Knowing the limitations of the development of luminescent films related to the aggregation-caused quenching effect(ACQ), compounds were synthesized with AIEE-like properties (aggregation-induced increased emission). The studies of its photophysical and electrochemical properties indicated that a compound with aryloxy-BTD-chalcone architecture presented the best results in which expressive increases were observed in fluorescence intensity (30x) and in fluorescence quantum yield (from 0.0070 to 0.143) with the aggregation. With these data, new analogs were synthesized respecting the aryloxy-BTD-chalcone (or -fluorene) with yields ranging from 42 to 79 percent. The new analogues also presented AIEE and were applied as emitting layers in bilayer structure OLEDs for evaluation and comparison of their electroluminescent performance. The association of cross-coupling and aldol condensation was also used as a strategy to produce new photosensitizers for DSSCs. To this end, D-pi-A-pi-A compounds were synthesized in which the terminal acceptor groups act as TiO2 anchors. The use of this type of structure facilitates the injection of electrons due to the directional transfer of electrons from the donor to the acceptor portion. Based on this, new derivatives of chalcones and BTDs were synthesized. The syntheses were performed in two steps resulting in yields of 35 to 44 percent. Electrochemical studies showed good HOMO, LUMO and band gap values for all compounds. The LUMO values were above the TiO2 semiconductor conduction range (-4.0 eV) which guarantees the necessary driving force for the directioning of electrons. In addition, the HOMO values of all compounds were lower than the redox potential of the electrolyte (-4.8 eV) generating a high driving force for dye regeneration. It was observed that the compounds absorb in a region close to 350 nm in different solvents, which makes their use as DSSCs difficult. Finally, in the last chapter, a new strategy was presented to obtain potentially bioactive molecules from the association between aldol condensations and coupling reactions. The alpha-beta unsaturated system of chalcone makes it an interesting platform for regio and stereoselective insertion of aryl substituents in the olefinic portion of the substrate. Based on a strategy of insertion of aryl moieties already described by our group, tamoxifen, a drug currently used in therapy for the treatment of some breast tumors, analogues were synthesized. Six products were synthesized via a Heck reaction, resulting in E/Z mixtures of approximately 50:50 and yields of 29 to 57 percent.

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Polyfluorenes are polymers with outstanding properties: They are semi-conducting, relatively rigid, quite stable chemically and thermally, easily substituted and therefore potentially soluble in numerous solvents and more importantly, they exhibit blue electro- and photoluminescence. For all these reasons, these polymers are the subjects of numerous academic and industrial researches. The first subject of this work deal with the design, the synthesis and the characterisation of polyfluorenes end-capped with perylene dicarboximide derivatives. These perylene moieties are able to interact by energy transfer under specific conditions of illumination, proximity and orientation. Their observation by single molecule spectroscopy permitted therefore to gain valuable information concerning the three-dimensional folding of single polyfluorene chains. To complete this study, the synthesis and characterisation of a perylene end-capped trimer of fluorene was performed. This structure being monodisperse, a finer analysis of the energy-transfer occurring between both perylene dyes could be accomplished, which confirmed the structural hypothesis made for the polymer. During these studies, it has been observed that, in addition to the energy transfer occurring between both perylene derivatives, another energy transfer occurs between the polyfluorene backbone and the perylene derivatives upon excitation of the first. This led to the idea of the synthesis of a polyfluorene bearing perylenes dicarboximide as side chains. This perylene-rich polyfluorene has been used to build a photovoltaic cell efficient in the wavelengths of both polyfluorene absorption and perylene carboximide absorption. Another subject of this work was the design, synthesis and characterisation of polyfluorenes bearing bulky phenoxy groups as side-chains. These polymers, due to their lower tendency toward aggregation, exhibited a better stability of their emission colour upon annealing. Similarly, a series of homo- and copolymers of fluorene bearing bulky and hole accepting triphenylamine substituants was synthesised and characterised. In addition to their improved colour stability in comparison with dialkylpolyfluorenes, the LEDs build with these materials exhibited a very low turn on voltage.

Phosphorescent organic light emitting diodes (PHOLEDs) based on efficient electrophosphorescent dopant, platinum(II)-pyridyltriazolate complex, bis[3,5-bis(2-pyridyl)-1,2,4-triazolato]platinum(II) (Pt(ptp)2) have been studied and improved with respect to power efficiency, external efficiency, chromacity and efficiency roll-off. By studying the electrical and optical behavior of the doped devices and functionality of the various constituent layers, devices with a maximum EQE of 20.8±0.2 % and power efficiency of 45.1±0.9 lm/W (77lm/W with luminaries) have been engineered. This improvement compares to devices whose emission initially could only be detected by a photomultiplier tube in a darkened environment. These devices consisted of a 65 % bis[3,5-bis(2-pyridyl)-1,2,4-triazolato]platinum(II) (Pt(ptp)2) doped into 4,4'-bis(carbazol-9-yl)triphenylamine (CBP) an EML layer, a hole transporting layer/electron blocker of 1,1-bis[(di-4-tolylamino)phenyl]cyclohexane (TAPC), an electron transport layer of 1,3,5-tris(phenyl-2-benzimidazolyl)-benzene (TPBI), and a LiF/Al cathode. These devices show the acceptable range for warm white light quadrants and qualify to be called "warm white" even w/o adding another emissive layer. Dual EML devices composed of neat Pt(ptp)2 films emitting orange and CBP: Pt(ptp)2 film emitting blue-green produced a color rendering index (CRI) of 59 and color coordinates (CIE) of (0.47,0.49) at 1000Cd/m² with power efficiency of 12.6±0.2 lm/W and EQE of 10.8±0.2 %. Devices with two blue fluorescent emission layers as singlet filters and one broad yellow emission layer from CBP: Pt(ptp)2 displayed a CRI of 78 and CIE of (0.28,0.31) at 100Cd/m² with maximum power efficiency of 6.7±0.3 lm/W and EQE of 5.7±0.2 %.

Organic light emitting diodes (OLEDs) are electronic devices made by sandwitching organic light emissive materials between two electrodes. When voltage is applied across the two conductors, a bright light is generated. The color of the emitting light depends on the band gap of the semiconducting material. The work described here focuses on designing and synthesizing narrow band gap molecular systems derived from fused-arene derivatives for producing organic blue light emitting diodes. Three molecular systems derived from anthracene, pyrene, and carbazole, were designed and synthesized. Two molecular systems of anthracen-9-ylmethyl anthracene-9- carboxylate and pyren-1-ylmethyl 4-bromobenzoate were synthesized through Steglich esterification reaction and the third, pyren-1-ylmethyl 4-(9-hexyl-6-{4-[(pyren-1- ylmethoxy) carbonyl] phenyl}-9H-carbazol-3-yl) benzoate was synthesized by Grignard metathesis followed by Kumada coupling reaction. Structural characterizations were performed using 1H, 13C NMR and FTIR analysis. Photophysical properties of these systems were studied in chloroform (CHCl3) solution using UV-visible and Fluorescence spectroscopies. The absorption and fluorescence emission spectra revealed the potential applicability of these three systems as blue and blue-green emitters for OLEDs. The future work of this project will focus on utilizing these three molecular systems to fabricate OLED devices.

Over the past decade, intensive academic and commercial interests have been paid on compounds possessing photochemical properties, namely for their preparation, chemical properties, high efficiency and potential low-cost. Compounds having intense photochemical properties gained great interest due to wide range of potential applications. The sensitizers are one of the key components for high power-conversion efficiency in the dye sensitized solar cells (DSSCs). They are the core components in the organic light-emitting devices (OLEDs) due to their ability to emit light with the wavelengths largely red- shifted from their absorption wavelength. Ruthenium based sensitizers have been tagged “molecular light switches” because, although the fluorescence of these complexes in aqueous solutions is negligible, it increases of greater than 10000 fold in the presence of DNA. Many polypyridyl and dipyrido phenazine ruthenium complexes have achieved high power conversion efficiencies and therefore are of practical interest. Several research groups stated that the dipyrido phenazine ligand may be thought of as comprising two components: a bipyridyl unit and a phenazine unit. These two subunits behave essentially separately, with many molecular orbitals being localised over only one subunit and a redox properties of central phenazine moiety in the dipyrido phenazine ligand are important for the photochemical applications. Therefore a phenazine ligand was selected as a model for the present investigation. The chemistry of phenazine ligand is mostly limited to the late transition metal and f - element complexes. Our laboratory has a rich backgroung in the aluminum and early transition metal chemistry. The aluminum chemistry and early transition metal chemistry are of great interest since aluminum and early transition metal complexes are environmentally friendlier and cheaper than the late transition metal compounds. Another drawback of the ruthenium-based sensitizers is the lack of absorption in the red region of the visible spectrum, and also low molar extinction coefficients. An essential requirement for efficient conversion of solar energy is the good spectral match of the sensitizer absorption to the emission spectrum of solar radiation. In this regard, the ruthenium sensitizers’ spectral response in the lower energy regions is not sufficient. The current project has three parts. In the first part we collected and reviewed known literature regarding the certain classes of non-innocent ligands containing the six-membered carbon- nitrogen heterocycles and regarding the ligands potentially important for the photochemical applications. We also reviewed all available to the data information about the complexes supported by the phenazine ligand. In the second part we have investigated interaction of alkylaluminum compounds and phenazine and observed reduction of phenazine accompanied by formation of dialuminum cage type compounds containing two formally mononegative phenazine ligand. The derivatization of phenazine has been also observed. It resulted in formation of compounds having a stable organic radical. In a third part of our project we have explored interaction of phenazine or thiophenazine with the alkylaluminum compounds and chromium dichloride. The reaction in the three component system resulted in reduction of phenazine ligand and lead to the heterometallic Cr(II) - aluminum complexes containing a formally dinegative phenazine or thiophenazine ligands. When a large excess of triethylaluminum was taken, reduction of phenazine and chromium has been observed leading to the heterometallic multinuclear Cr(I) - aluminum complex containing a formally dinegative phenazine ligands and two chromium atoms in one complex in the rare oxidation state one.