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.

Visando o crescente interesse em pesquisa de novos materiais para a fabricação de dispositivos eletrônicos a base de polímeros semicondutores, com elevado potencial para a fabricação de diodos emissores de luz poliméricos os (PLEDs - Polymer light-emitting diodes), este presente trabalho teve como objetivo a síntese de novos copolímeros através da reação de acoplamento de Suzuki e a sua fabricação de PLEDs com esses novos materiais. É conhecido que um dos grandes problemas na fabricação desses dispositivos é propiciar um maior número de recombinações elétrons/ lacunas no interior de suas camadas ativas com a finalidade de aumentar a emissão de luz visivel. Para amenizar esse problema os copolímeros sintetizados tiveram como finalidade unir num único material, a propriedade de transporte de elétrons associada à boa emissão de luz. O objetivo final foi elevar a injeção de elétrons contribuindo para aumentar o número de recombinações dos pares elétrons/lacunas, resultando em aumento de eletroluminescência e de eficiência dos dispositivos. Os copolímeros inéditos foram sintetizados e caracterizados por ressonância magnética nuclear hidrogênio, termogravimetria, calorimetria diferencial exploratória, espectroscopia no UV-Vis e no infravermelho, fluorimetria no UV-vis, cromatografia de permeação em gel e voltametria cíclica. Os copolímeros foram também utilizados como camada ativa na construção de uma série de PLEDs com arquiteturas diferentes, tanto puro como em mistura com o poli(N-vinilcarbazol) (PVK), ou, ainda, utilizando tris-8-hidroxiquinolina alumínio (Alq3) como camada transportadora de elétrons ( ETL - Electron transport layer). Os dispositivos foram caracterizados quanto ao comportamento elétrico, pelas curvas de corrente por tensão (IxV), e à sua eletroluminescência. Os PLEDS fabricados com os copolímeros sintetizados mostraram que não necessitam do uso de uma camada transportadora de elétrons, ETLs, adicional. / Polymer light-emitting diodes (PLEDs) have been heavily researched since their initial fabrication and utilization. In order to improve the efficiency of polymeric light-emitting devices, new materials have been studied. This present study focuses in the preparation of new copolymers by Suzuki coupling reaction and then evaluate the copolymers as active layer in PLEDs. It is well known that the performance of PLEDs is still limited by the number of electron/hole recombination. To overcome this problem, a new material is proposed to integrate the functions of n charge carrier and light emission through copolymerization. Novel copolymers were synthesized and characterized by hydrogen nuclear magnetic resonance, thermogravimetry, and differential scanning calorimetry, UVVis, Fluorescence and IR spectroscopy, GPC and cyclic voltammetry. Copolymers thus prepared were used as active layer in a series of PLEDs with different architectures, pure and in blends with poly(N-vinylcarbazole) (PVK), as well as with tris-8 hydroxyquinoline aluminum (Alq3) as an extra electron transport layer. The devices were characterized concerning their electrical behavior, by the characteristic J-V diode curves, and their electroluminescence. It was demonstrated that the PLEDs built with the synthesized copolymers do not need an extra ETL.

Utilizando a reação de acoplamento de Suzuki, novos polímeros e copolímeros semicondutores com elevado potencial para a fabricação de PLEDs foram sintetizados, tendo como finalidade unir em uma única camada emissiva, na forma de copolímeros ou na forma de blendas, materiais com propriedades transportadoras e injetoras de elétrons; grupos quinolina associados a materiais com elevadas propriedades de emissão de luz contendo grupos fluoreno. Esses copolímeros sintetizados, todos ainda não descritos na literatura ou em patentes, apresentaram rendimentos acima de 70% e rendimentos quânticos de fotoluminescência entre 60% e 83%, foram utilizados como camada emissiva na construção de PLEDs. Estes PLEDs foram caracterizados quanto ao seu comportamento elétrico através da obtenção de curvas de corrente em função da tensão (IxV) e dos espectros de eletroluminescência. Os resultados mostraram que a incorporação da quinolina aos copolímeros aumentou a sua estabilidade térmica, observada pela temperatura de inicio de degradação que elevou-se em até 80°C. Nos PLEDs, houve melhorias no balanceamento de cargas, dispensando até mesmo a deposição de uma camada adicional transportadora de elétrons (ETL). As tensões de operação desses dispositivos ficaram entre 2,0 e 5,2 V, com emissão entre 525 e 590nm. Esses materiais também tiveram as suas estruturas caracterizadas por ressonância magnética nuclear de hidrogênio, termogravimetria, calorimetria diferencial exploratória, espectroscopias no UV-Vis e no infravermelho, fluorimetria no UV-vis e cromatografia de permeação em gel. Filmes Langmuir e Langmuir- Blodgett dos copolímeros foram preparados e caracterizados por espectroscopia com luz polarizada de reflexão e absorção no infravermelho (PM-IRRAS) e por microscopia de força atômica (AFM). / New polymers and copolymers with a high potential for PLEDs constructions have been synthesized by Suzuki reaction and aims together in a single emissive layer in the form of copolymers or blended, materials with transporting and electron injection properties; quinoline groups linked to materials with high light emission properties as fluorene group. All these copolymers have not been described in literature or in patents, presented yields above 70%, quantum yields between 60% and 83% and were used as emissive layer in PLEDs. These PLEDs were characterized concerning their electrical behavior, by the characteristic J-V diode curves, and their electroluminescence. The results showed that the presence of quinoline increased its thermal stability at around 80° C and the PLEDs built with the synthesized copolymers do not need an extra ETL. The operating voltages of these devices were observed between 2.0 and 5.2 V with EL emission between 525 and 590nm. These new materials were also characterized by hydrogen nuclear magnetic resonance, thermogravimetry, differential scanning calorimetry, UV-Vis, Fluorescence and IR spectroscopy and gel permeation chromatography. Langmuir e Langmuir-Blodgett films were made and characterized by Polarization-Modulation Infrared Reflection-Absorption Spectroscopy (PM-IRRAS) and atomic force microscopy (AFM).

Thesis (Ph.D.)--University of Missouri-Columbia, 2006. / The entire dissertation/thesis text is included in the research.pdf file; the official abstract appears in the short.pdf file (which also appears in the research.pdf); a non-technical general description, or public abstract, appears in the public.pdf file. Title from title screen of research.pdf file viewed on (February 28, 2007) Vita. Includes bibliographical references.

Utilizando a reação de acoplamento de Suzuki, novos polímeros e copolímeros semicondutores com elevado potencial para a fabricação de PLEDs foram sintetizados, tendo como finalidade unir em uma única camada emissiva, na forma de copolímeros ou na forma de blendas, materiais com propriedades transportadoras e injetoras de elétrons; grupos quinolina associados a materiais com elevadas propriedades de emissão de luz contendo grupos fluoreno. Esses copolímeros sintetizados, todos ainda não descritos na literatura ou em patentes, apresentaram rendimentos acima de 70% e rendimentos quânticos de fotoluminescência entre 60% e 83%, foram utilizados como camada emissiva na construção de PLEDs. Estes PLEDs foram caracterizados quanto ao seu comportamento elétrico através da obtenção de curvas de corrente em função da tensão (IxV) e dos espectros de eletroluminescência. Os resultados mostraram que a incorporação da quinolina aos copolímeros aumentou a sua estabilidade térmica, observada pela temperatura de inicio de degradação que elevou-se em até 80°C. Nos PLEDs, houve melhorias no balanceamento de cargas, dispensando até mesmo a deposição de uma camada adicional transportadora de elétrons (ETL). As tensões de operação desses dispositivos ficaram entre 2,0 e 5,2 V, com emissão entre 525 e 590nm. Esses materiais também tiveram as suas estruturas caracterizadas por ressonância magnética nuclear de hidrogênio, termogravimetria, calorimetria diferencial exploratória, espectroscopias no UV-Vis e no infravermelho, fluorimetria no UV-vis e cromatografia de permeação em gel. Filmes Langmuir e Langmuir- Blodgett dos copolímeros foram preparados e caracterizados por espectroscopia com luz polarizada de reflexão e absorção no infravermelho (PM-IRRAS) e por microscopia de força atômica (AFM). / New polymers and copolymers with a high potential for PLEDs constructions have been synthesized by Suzuki reaction and aims together in a single emissive layer in the form of copolymers or blended, materials with transporting and electron injection properties; quinoline groups linked to materials with high light emission properties as fluorene group. All these copolymers have not been described in literature or in patents, presented yields above 70%, quantum yields between 60% and 83% and were used as emissive layer in PLEDs. These PLEDs were characterized concerning their electrical behavior, by the characteristic J-V diode curves, and their electroluminescence. The results showed that the presence of quinoline increased its thermal stability at around 80° C and the PLEDs built with the synthesized copolymers do not need an extra ETL. The operating voltages of these devices were observed between 2.0 and 5.2 V with EL emission between 525 and 590nm. These new materials were also characterized by hydrogen nuclear magnetic resonance, thermogravimetry, differential scanning calorimetry, UV-Vis, Fluorescence and IR spectroscopy and gel permeation chromatography. Langmuir e Langmuir-Blodgett films were made and characterized by Polarization-Modulation Infrared Reflection-Absorption Spectroscopy (PM-IRRAS) and atomic force microscopy (AFM).

Visando o crescente interesse em pesquisa de novos materiais para a fabricação de dispositivos eletrônicos a base de polímeros semicondutores, com elevado potencial para a fabricação de diodos emissores de luz poliméricos os (PLEDs - Polymer light-emitting diodes), este presente trabalho teve como objetivo a síntese de novos copolímeros através da reação de acoplamento de Suzuki e a sua fabricação de PLEDs com esses novos materiais. É conhecido que um dos grandes problemas na fabricação desses dispositivos é propiciar um maior número de recombinações elétrons/ lacunas no interior de suas camadas ativas com a finalidade de aumentar a emissão de luz visivel. Para amenizar esse problema os copolímeros sintetizados tiveram como finalidade unir num único material, a propriedade de transporte de elétrons associada à boa emissão de luz. O objetivo final foi elevar a injeção de elétrons contribuindo para aumentar o número de recombinações dos pares elétrons/lacunas, resultando em aumento de eletroluminescência e de eficiência dos dispositivos. Os copolímeros inéditos foram sintetizados e caracterizados por ressonância magnética nuclear hidrogênio, termogravimetria, calorimetria diferencial exploratória, espectroscopia no UV-Vis e no infravermelho, fluorimetria no UV-vis, cromatografia de permeação em gel e voltametria cíclica. Os copolímeros foram também utilizados como camada ativa na construção de uma série de PLEDs com arquiteturas diferentes, tanto puro como em mistura com o poli(N-vinilcarbazol) (PVK), ou, ainda, utilizando tris-8-hidroxiquinolina alumínio (Alq3) como camada transportadora de elétrons ( ETL - Electron transport layer). Os dispositivos foram caracterizados quanto ao comportamento elétrico, pelas curvas de corrente por tensão (IxV), e à sua eletroluminescência. Os PLEDS fabricados com os copolímeros sintetizados mostraram que não necessitam do uso de uma camada transportadora de elétrons, ETLs, adicional. / Polymer light-emitting diodes (PLEDs) have been heavily researched since their initial fabrication and utilization. In order to improve the efficiency of polymeric light-emitting devices, new materials have been studied. This present study focuses in the preparation of new copolymers by Suzuki coupling reaction and then evaluate the copolymers as active layer in PLEDs. It is well known that the performance of PLEDs is still limited by the number of electron/hole recombination. To overcome this problem, a new material is proposed to integrate the functions of n charge carrier and light emission through copolymerization. Novel copolymers were synthesized and characterized by hydrogen nuclear magnetic resonance, thermogravimetry, and differential scanning calorimetry, UVVis, Fluorescence and IR spectroscopy, GPC and cyclic voltammetry. Copolymers thus prepared were used as active layer in a series of PLEDs with different architectures, pure and in blends with poly(N-vinylcarbazole) (PVK), as well as with tris-8 hydroxyquinoline aluminum (Alq3) as an extra electron transport layer. The devices were characterized concerning their electrical behavior, by the characteristic J-V diode curves, and their electroluminescence. It was demonstrated that the PLEDs built with the synthesized copolymers do not need an extra ETL.

A novel synthetic methodology has been developed for attaching fluorene derivatives, containing different types of electron donating and accepting groups at the 2 and 7 positions, to gold nanoparticles of different sizes by exploiting the affinity of the thiol functional group for gold. The distance between the dye and nanoparticles was varied by introducing two alkyl chains containing different number of carbon atoms at the 9 position on the fluorene ring system. The methodology that was developed gave enough scope for performing Radiative Decay Engineering (RDE) studies, in order to investigate the impact of gold nanoparticles on the singlet oxygen quantum yields of fluorene dyes that already exhibit high singlet oxygen quantum yields as well as high two photon absorption (2PA) cross-sections. The dialkylation of the fluorene derivatives was accomplished by reacting the dye with [alpha], [omega]-dibromoalkanes containing different number of carbon atoms in a biphasic reaction mixture containing toluene and aqueous sodium hydroxide solution in the presence of tetrabutylammonium bromide (TBAB) as a phase transfer catalyst. The bromine atom on the alkyl chains was converted to thioester by reaction with potassium thioacetate. This was followed by the hydrolysis of the thioester to form the thiol moiety. The compounds synthesized were characterized using 1H and 13C nuclear magnetic resonance (NMR) spectroscopy and elemental analysis. Functionalization of gold nanoparticles was attempted by bringing into contact a solution of the thiol compound in toluene and an aqueous gold nanoparticles solution. UV-vis absorbance spectroscopy was used to monitor the progress of the attachment. Surface Enhanced Raman Scattering (SERS) spectroscopy was used to probe the enhancement of Raman signal by the metallic nanoparticles.

The possibility ofusing two-photon absorbing compounds to treat cancer is very attractive for a number ofreasons. These reasons include the preferred use ofa nondamaging, near-IR light source, reduced light scattering, and a better depth ofpenetration with possible three-dimensional resolution. Although work has been done which demonstrates the possible utility oftwo-photon photodynamic therapy, the field is still in its infancy for two main reasons. The first is a general lack oftwo-photon absorbing materials for use in photodynamic therapy. The other is the organic nature ofthese dyes, which makes them difficult to get into the cell. The work outlined in this thesis is two-fold and designed to further the knowledge base in two-photon photodynamic therapy through investigations with new two-photon absorbing organic compounds. Several organic compounds were encapsulated in liposomes and introduced to tumor cells. The strate~y for encapsulating and evaluating these compounds was three fold. First we had to confirm encapsulation with fluorescence microscopy. The next 'Step was to verify cellular uptake and asses "dark" cytotoxicity. Finally, we needed to verify photodynamic therapeutic activity. Results of these three main experiments are presented, and provide the foundation for continued 11 research in this most promising field. The details surrounding the synthesis and evaluation ofa model compound are also presented. 111

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.<p>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. <p>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. <p> / Doctorat en sciences, Spécialisation chimie / info:eu-repo/semantics/nonPublished

Described herein are three projects centered on the synthesis of conducting polymer derivatives for various applications. The first is the novel synthesis of 9,9-dioctylfluorene-co-benzothiadiazole [F8BT] oligomers through solid phase synthesis for the study of the thermodynamics and kinetics of electron transfer in the polymer. The second endeavor involves the synthesis of a series of 4”,3’’’-dialkyl-2,2’:5’,2”:5”,2’’’:5’’’,2’’’’:5’’’’,2’’’’’-sexithiophenes for the studies on crystal packing and surface deposition of organic p-type semiconducting materials. Lastly is described the development of a conducting metallopolymer based on the ligand 2,6-Bis(4-(2,2’-bithiophen-5-yl)-1H-pyrazol-1-yl)pyridine for use in a drug delivery system. / text