Carbon nanotubes are carbon based structures with outstanding electronical and mechanical properties. They are used in a wide range of applications, usually embedded in polymer in the form of composites, in order to affect the electronic behavior of the matrix material. However, as the nanotubes properties are directly dependent on their intrinsic structure, it is necessary to select specific nanotubes depending on the application, which can be a complicated and inefficient process. This makes it attractive to be able to reduce the amount of material used in the composites. In this thesis, focus is placed on the electrical properties of the composites. A simple patterning method is presented which allows the use of extremely low amounts of nanotubes in order to increase the electrical conductivity of diverse polymers such as polystyrene (PS) or poly(3-hexylthiophene) (P3HT). This method is called nanoimprint lithography and uses a flexible mold in order to pattern composite films, leading to the creation of conducting nanotube networks, resulting in vertically conducting samples (from the bottom of the film to the top of the imprinted patterns). In parallel, X-ray diffraction measurements have been conducted on thin P3HT polymer films. These were prepared on either silicon substrate or on graphene, and the influence of the processing conditions as well as of the substrate on the crystallinity of the polymer have been investigated. The knowledge of the crystalline structure of P3HT is of great importance as it influences its electronic properties. Establishing a link between the processing conditions and the resulting crystallinity is therefore vital in order to be able to make opto-electronic devices such as transistor or photovoltaic cells.

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

Polyheterocycles such as polythiophene and its derivatives comprise an important class of conducting polymers used for electronic applications. They have been of great interest for use in electronic materials due to their increased environmental stability as well as novel electronic properties in their polymer states. We have been interested in exploring the electronic properties of organometallic analogues of the low-band-gap polymer poly(benzo[3,4-c]thiophene) (polyisothianaphthene) that incorporates η5-cyclopenta[c]thienyl monomers such as ferroceno[c]thiophene. First chapter of this dissertation involved synthetic attempts to ferroceno[c]thiophene. Exploring a shorter synthetic route to starting material, 1,2-di(hydroxymethyl)ferrocene was the first task. This was followed by attempts to synthesize an important precursor, 1,3-dihydroferroceno[c]thiophene to our target molecule, ferroceno[c]thiophene. In order to achieve our target precursor molecule, 1,3-dihydroferroceno[c]thiophene, we reacted 1,2-di(hydroxymethyl)ferrocene with H2S/H2SO4 and Na2S/HBF4 respectively. Reaction of 1,2-di(hydroxymethyl)ferrocene with either H2S/H2SO4 or Na2S/HBF4 results in 2,16-dithia[3.3](1,2)ferrocenophane instead of monomeric 1,3-dihydroferroceno[c]thiophene. Dehydration of 1,2-di(hydroxymethyl)ferrocene with dilute H2SO4 resulted in 2,16-dioxa[3.3](1,2)ferrocenophane. Formation of the five-membered tetrahydrothiophene or tetrahydrofuran rings is probably disfavored compared to formation of the ten-membered ferrocenophane rings because of greater strain in the five-membered rings. Thus, in order to achieve our target molecule ferroceno[c]thiophene, we took an alternate route. We decided to pursue the route with 1,4-dihydro-2,3-ferrocenodithiin being the precursor to our final target molecule. This was successfully accomplished. 1,2-Di(hydroxymethyl)ferrocene reacts with thiourea in the presence of catalytic trifluoroacetic acid to give a water-soluble thiouronium salt, which reacts with aqueous potassium hydroxide in air to give 1,4-dihydro-2,3-ferrocenodithiin, via oxidation of the intermediate 1,2 di(mercaptomethyl)ferrocene. 1,4-dihydro-2,3-ferrocenodithiin, an important precursor to our desired heterocyclic chemistry was synthesized. The increased emission of CO2, a greenhouse gas, to the atmosphere is a matter of serious worldwide concern. Every year a few gigatons of CO2 are added to the atmosphere by various anthropogenic activities like burning of fuel for electricity, running industry and transportation. Thus, developing ways to reduce the emission of CO2 to the atmosphere is of major importance. Although the amine-based absorption method is considered the most reliable, it is an expensive alternative. The catalyzed enhancement of CO2 absorption is a critical component to reduce the capital cost of CO2 capture. Specifically, an effective catalyst will increase the CO2 hydration rate, thereby decreasing the size of the absorber tower needed. In biological systems, CO2 hydration is catalyzed by the enzyme carbonic anhydrase, which contains ZnII in its active site. Carbonic anhydrase typically is not stable enough to be used in an industrial process, therefore, there is a need to synthesize robust, inexpensive CO2 hydration catalysts. Majority work of this dissertation focuses on designing catalysts that show high CO2 hydration rate similar to carbonic anhydrase while showing superiority towards temperature, pH and inhibitors. We focused our efforts on complexes of Zn, Cu and Co with ligands such as 1,4,7,10-tetraazacyclododecane (cyclen), 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane (teta and tetb), tris(benzimidazolylmethyl)amine (BIMA) and anionic tris(pyrazolylborate)s that mimic the enzyme, carbonic anhydrase. Several of these complexes have been reported for their interesting CO2 capture properties but they contain hazardous perchlorate ion. We desired to replace them with benign, non-coordinating counterions like PF6-, BF4-, Cl-, CH3COO-, NO3-, CF3SO3-, SiF62- that avoid the potentially explosive perchlorate salts. In order to test the activity of synthesized catalysts under industrial capture conditions, we designed a quick experimental screening pH drop method. [[Zn(cyclen)(H2O)][SiF6]•2H2O as well as a number of other catalysts have been synthesized and tested for their post-combustion CO2 capture enhancement capabilities in aqueous solvent mixtures under both pH-drop screening and stopped-flow conditions. [Zn(cyclen)(H2O)][SiF6]•2H2O, which has an unreactive counteranion, is found to catalyze CO2 hydration in aqueous solvent mixtures under both pH-drop screening and stopped-flow conditions. However, under pH-drop which has conditions similar to industrial post combustion capture, activity of Zn(cyclen)(H2O)][SiF6]•2H2O drops as compared to observed in stopped-flow conditions probably because of bicarbonate coordination to Zn active site in these systems. The Zn center is highly electron deficient and therefore easily coordinates anions, inhibiting the ability to reform hydroxyl species on the metal. Thus, we decided to test the catalysis of benchmark enzyme carbonic anhydrase under similar conditions to determine the threshold value. Carbonic anhydrases catalyze the hydration of carbondioxide at ambient temperatures and physiological pH with the highest known rate constant= 106 M–1 s–1, but in our system (CAER pH drop screening) came out to be 438797 M–1 s–1. The lower catalytic rate constant for carbonic anhydrase in 0.1000 M K2CO3, similar to Zn-cyclen, strengthens the conjecture that at high bicarbonate concentrations, HCO3– binding to the Zn(II) active site slows catalysis by inhibiting bicarbonate displacement with water to regenerate the active species. The complexes containing anionic ligands that donate electron density into the metal center may serve to remove anionic bicarbonates/carbamates from the secondary coordination sphere and away from the metal center, thereby facilitating bicarbonate/anion dissociation and increasing CO2 hydration rates. We studied catalysis of trispyrazolylborate molecule in 30% MEA and found the molecule to be catalytically active. We also developed an NMR-based method to see if the coordination of solvents to CO2 capture solvents can be studied.

[Truncated abstract] Chapter 1 provides an introduction to the 'sarcophagine' class of ligands and the field of metallopolymers. The synthesis, stereochemistry, physical properties and functionalisation of 'sarcophagines' and their metal complexes are discussed. A brief overview of the burgeoning field of metallopolymers is given with specific mention of the synthetic routes to pendant metallopolymers, and how these could be employed to prepared cage amine containing metallopolymers. Chapter 2 deals with the synthesis, characterisation and reactivity of cinnamylamino and styrylamido derivatives of the cage amines [Co((NH2)2sar)]3+, [Co((CH3)(NH2)sar)]3+ and [Cu((NH2)2sar)]2+. The cinnamylamino derivatives were prepared using reductive alkylation of the aforementioned amines with cinnamaldehyde. Procedures were developed to isolate the complexes without causing unwanted additions to the double bond. The cinnamylamino derivatives displayed unexpected reactivity towards a range of reducing agents, resulting in unexpected reduction of the double bond and cleavage of the cinnamyl group, but ultimately in the preparation of phenylpropylamino derivatives of [Co((NH2)2sar)]3+ and [Co((CH3)(NH2)sar)]3+. Attempts to rationalise the reactivity of the double bond have been explored based upon the physical properties and reactivity of the double bond. The styrylamido derivatives were prepared by treatment of the cage amines with 4-vinylbenzoyl chloride, and the complexes isolated in a similar manner to those of the cinnamylamino derivatives to ensure the amide linkage remained intact. Most of the complexes have been structurally characterised. ... Both the 2-thienyl and 3-thienyl derivatives of [Co((NH2)2sar)]3+ and [Co((CH3)(NH2)sar)]3+ have been prepared using reductive alkylation with the respective carboxaldehydes of thiophene. One of the optically pure isomers has been prepared. The complexes have been fully characterised including structural characterisation. Polymerisation of the thiophene-cage amine complexes was investigated under a range of chemical and electrochemical conditions, though polymerisation was never observed. Cleavage of the thienyl groups was observed when ceric ammonium nitrate in nitric acid was used as the oxidant. The attachment of oligothiophenes and mixed pyrrole-thiophene oligomers to cage amines were investigated using reductive alkylation and various pyrrole ring-forming reactions about the apical amino groups, though none of the desired complexes were isolated, reasons for the lack of reactivity were discussed. An efficient synthesis of N-(4-benzoic acid)- 2,5-di(2-thienyl)pyrrole was developed and was shown to the electropolymerisable, albeit the polymer films were non-conducting. Attempts to couple N-(4-benzoic acid)- 2,5-di(2-thienyl)pyrrole with a cage amine via its acid chloride were complicated by decomposition reactions, the nature of one of these products is discussed. Chapter 5 presents investigations into the preparation of simple complexes containing multiple cage amines using alkylation and acylation procedures with aromatic substrates. The complexes were found to exhibit some interesting electrochemical and chemical properties, demonstrating that even simple multiple cage amine species can display complicated and interesting behaviour.

Intrinsically conducting polymers (ICPs) with high mechanical strength and electrical conductivity are attractive for several applications spanning the fields of energy, defense, and transportation. Electrochemically processed polythiophene (PTh) films are a class of ICPs that have been demonstrated recently to possess electrical conductivities as high as 1,300 S/cm and be stronger than common types of processed aluminum foils. While these results are promising, the electrical conductivity of PTh is still low compared to metals and the effects of important process conditions such as electrode resistance, distance between working and counter electrodes, and thiophene concentration on the structure and physical properties of electrochemically processed PTh films must be investigated in detail. In this work, electrode resistance and inter-electrode distance were demonstrated to be inversely proportional to the charge efficiency for PTh film growth. A critical concentration of thiophene that produced films with the highest conductivity was also revealed. Anionic surfactants sodium dodecyl sulfate (SDS) and sodium dodeclybenzene sulfonate (SDBS) were used, with and without a proton scavenger, in the Lewis acid boron trifluoride diethyl etherate (BFEE) electrolyte, which allows polymerization of thiophene at low oxidation potentials, to enhance the ordering and conjugation length of PTh through stabilization of the radical cation of thiophene via the dodecyl chain of the anionic surfactants. X-ray diffraction spectra revealed enhanced order and packing when surfactant was used during the processing of PTh films, and measured electrical conductivities were increased by as much as 300% because of the surfactant-mediated structural improvements. Necking behavior observed in tensile test of PTh films with anionic surfactant additives also suggests chain alignment and increased chain length.

Eine Reihe 3-(p-X-phenyl)-Thiophenmonomeren (X = -H, -CH3, -OCH3, -COCH3, -COOC2H5, -NO2) wurde elektrochemisch polymerisiert, um Filme zu erhalten, die umkehrbar reduziert und oxidiert werden konnten (n-und p-dotiert wurden). Die Oxidationspotentiale der Monomere und die formalen Potentiale der n und p-Dotierprozesse der Polymere wurden mit Resonanz- und induktiven Effekten der Substituenten (Hammett konstanten) am Phenylring sowie semiempirisch errechneten Bildungswärmen der Monomereradikalkationen korreliert. Außerdem wurden die Oxidationspotentiale mit den Ionisierungspotentialen der Monomere verglichen, die über die Dichtefunktionialtheorie (DFT) errechnet wurden, die der Energie für das Erzeugen der Radikalkationen entsprechen. Um theoretische Grundlagen für die Einstufen-Bildung regioregulär -konjungierter Oligo- und Polythiophene zu erhalten, wurden die elektronischen Zustände von 3-Phenylthiophen-Derivaten anhand von Molekülorbitalberechnungen auf Grundlage der Dichtefunktionaltheorie mit Becke’s Drei-Parameter-Funktion (B3LYP), sowie mit den Basissätzen 6-31G(d) und 3-21G(d) erklärt. Die Reaktivität der Verknüpfung von mono- und oligo-3-Phenylthiophenen wurde von den berechneten ungepaarten Elektronenspindichten der entsprechenden Radikal-Anionen abgeleitet. Die Ionisierungspotentiale, die den Energien zur Erzeugung der Radikal-Anionen während der Oxidation entsprechen, wurden abgeschätzt. Die aus den 3-Phenylthiophenen entstandenen regioselektiven Hauptprodukte können gut durch die Größe der Spindichten erklärt werden. Da die Verknüpfungsreaktion an der zwei-Position des Thiophnrings (C-2) sterisch durch die Phenylgruppe und den Thiophenring gehindert ist, startet die Initiierung der 3-Phenylthiophene über die Bildung eines Kopf-Schwanz-Dimers. Folglich spielt das Kopf-Schwanz-Dimer eine wichtige Rolle bei den Wachstumsreaktionen der 3-Phenylthiophene. Die Ursache dafür liegt darin, dass das Kopf-Schwanz-Dimer in 5-Position die höchste Spin-Dichte besitzt und die Wahrscheinlichkeit einer Kopf-Kopf-Verknüpfung aufgrund der sterischen Hinderung zwischen dem Thiophenring und der Phenylgruppe gering ist. Polymerfilme von 3-Phenylthiophenderivaten, die durch elektrochemische Polymerisation synthetisiert wurden, sind in situ und ex situ durch Resonanz-Raman-Spektroskopie bei verschiedenen Anregungswellenlängen, sowie durch in situ und ex situ UV-Vis Spektroskopie analysiert wurden. Die Entwicklung der in situ UV-Vis-Spektren der Polymer von 3-Phenylthiophene nach der Dotierung wird durch ähnliche Eigenschaften gekennzeichnet, wie für viele Polythiophene mit einem hohen Grad der Konjugation beobachtet. Während der schrittweisen Oxidation der Poly-3-phenylthiophen Filme verringert sich die Intensität der Absorption wegen des Überganges bei 450-566 nm und ein neues ausgedehntes Absorptionsband, das auf (bi)polaron Zustände bezogen wird erscheint bei ungefähr 730-890 nm. Andererseits wird während der Oxidation (p-Dotierung) des Poly3-phenylthiophen Filmes eine blau/hypsochrome Verschiebung für beide Absorptionsbänder beobachtet . Es wird durch die Tatsache erklärt, dass ein Polymer eine Verteilung der Kettenlängen enthält und die längste Polymer kette (dessen Absorption bei niedriger Energie auftritt), bei niedrigeren Potentialen zu oxidieren beginnt. Die elektrochemischen Bandlücken der Derivate von 3-Phenylthiophen sind durch zyklische Voltametrie gemessen worden. Der Effekt der Substituenten auf den Oxidations-/Reduktions- potentiale wird besprochen. Bei Bandlücken, die durch zyklische Voltammetrie erhalten wurden, hat sich herausgestellt, dass sie im Allgemeinen höher liegen als optische Bandlücken. Erste Resultate der in situ Resonanz-Raman-Spektroskopie, von dem elektrochemisch erzeugten Polymerderivate von 3-Phenylthiophen Filmen auf einer Platinelektrode, in einer organischen Elektrolytlösung, werden berichtet. Beobachtete Raman Banden werden zugewiesen; gegründet auf diesen Resultaten werden die zuvor angenommenen molekularen Strukturen diskutiert. / A series of 3-(p-X-phenyl) thiophene monomers (X= –H, –CH3, –OCH3, –COCH3, –COOC2H5, –NO2) was electrochemically polymerized to furnish polymer films that could be reversibly reduced and oxidized (n- and p-doped). The oxidation potentials of the monomers and formal potentials of the n- and p-doping processes of polymers were correlated with resonance and inductive effects (Hammett constants) of the substituents on the phenyl ring as well as the semiempirically calculated heats of formation of the monomer radical cations. Moreover, the oxidation potentials of the monomers were correlated with the ionization potentials of the monomers calculated via density functional theory (DFT), which correspond to the energies for generating radical cations during oxidative processes. For obtaining a theoretical basis for the one-step formation of regioregular –conjugated oligo-and polythiophenes, the electronic states of 3-phenylthiophene derivatives were elucidated by molecular orbital calculations using density functional theory with the Becke-type three parameters functional (B3LYP), the 6-31G(d), and 3-21G(d) basis sets. The reactivity for coupling reaction of mono- and oligo-3-phenylthiophenes are inferred from the calculated unpaired electron spin densities of the respective radical cations, and the ionization potentials which correspond to the energies for generating radical cations during oxidative processes were estimated. The major regioselective products of the oligomerization of 3-phenylthiophene can be well understood in terms of the magnitude of spin densities. Since the steric hindrance between the phenyl group and thiophene ring interferes with the coupling reaction occurring between 2-postions (C–2) of thiophene rings, the initiating reaction of 3-phenylthiophene is generaton of a head-to-tail (HT) dimer. Thus, the head-to-tail (HT) dimer plays an important role in the propagation reactions of 3-phenylthiophene. This originates from the highest spin density at the 5- position of the HT dimer and low probability of the HH coupling due to the steric hindrance between thiophene ring and phenyl group. Polymer films of the 3-phenylthiophene derivatives prepared by electrochemical polymerization were analyzed, in situ and ex situ, with resonance Raman spectroscopy using several excitation wavelengths as well as in situ and ex situ UV-Vis-spectroscopy. The evolution of the in situ UV-Vis-spectra of poly 3-phenylthiophene derivatives upon doping is characterized by similar features as observed for many polythiophenes with high degree of conjugation. During stepwise oxidation of the poly-3-phenylthiophene films the intensity of the absorption due to the transition around 450–566 nm decreases and a new broad absorption band related to (bi)polaron states appears around 730-890 nm. On the other hand, during the oxidation (p-doping) of the poly-3-phenylthiophene films a blue/hypsochromic shift is observed for both absorption bands. It is explained by the fact that a polymer contains a distribution of chain lengths, and the longest polymer chains (the absorption of which occurs at lower energies) start to oxidize at lower potentials. The electrochemical bandgaps of 3-phenylthiophene derivatives have been measured by cyclic voltammetry. The effect of substituents on the oxidation / reduction potentials is discussed. Bandgaps obtained by cyclic voltammetry have been found to be in general higher than optical bandgaps. Preliminary results of in situ resonance Raman spectroscopy of electrochemically generated poly-3-phenylthiophene derivatives films on a platinum electrode exposed to an organic electrolyte solution are reported. Observed Raman bands are assigned; based on these results previously suggested molecular structures are discussed.

In the first part of this work, the structural and thermal characteristics of polyacrylonitrile, polyacrylonitrile films treated under the electrolysis conditions in the absence of thiophene, polythiophene and the mechanical mixture and a conducting copolymer of polyacrylonitrile/polythiophene have been studied by pyrolysis mass spectrometry technique. The thermal degradation of polyacrylonitrile occurs in three steps / evolution of HCN, monomer, low molecular weight oligomers due to random chain cleavages are followed by cyclization and dehydrogenation reactions yielding crosslinked and unsaturated segments. Pyrolysis of the treated polyacrylonitrile films indicated decrease in the yields of monomer and oligomers, and increase in the amount of products stabilized by cyclization reactions were detected. Polythiophene degrades in two steps / the loss of the dopant and degradation of polymer backbone. The evolution profiles of polythiophene based products from polythiophene/polyacrylonitrile showed nearly identical trends with those recorded during the pyrolysis of pure polythiophene. However, evolution of HCN and the degradation products due to the homolytic cleavages of the polymer backbone continued through out the pyrolysis indicating a significant increase in their production. Furthermore, the yield of thermal degradation products associated with decomposition of the unsaturated cyclic imine segments decreased. A careful analysis of the data pointed out presence of mixed dimers confirming copolymer formation. In the second part of this work, a poly(acrylonitrile-co-butadiene) sample involving monomer units having quite similar molecular weights have been analyzed to investigate the limits of the pyrolysis mass spectrometry technique. Pyrolysis of aged poly(acrylonitrile-co-butadiene) indicated oxidative degradation of the sample. Keywords: conducting copolymer, polyacrylonitrile, polythiophene, polybutadiene, direct pyrolysis mass spectrometry

ABSTRACT CHARACTERIZATION OF CONDUCTING POLYMERS OF ESTER LINKAGE CONTAINING THIOPHENE DERIVATIVES VIA MASS SPECTROSCOPY Aslan, Evren M.Sc., Department of Chemistry Supervisor: Prof. Dr. Levent Toppare Co-Supervisor: Prof.Dr. Jale Hacaloglu December 2004, 86 pages In order to investigate the thermal and structural characteristics of terepthalic acid bis-(2-thiophen-3-yl-ethyl)ester (TATE), decanedioic acid bis-(2-thiophen-3-yl- ethyl) ester (DATE) and octanoic acid 2-thiophen-3-yl-ethyl ester (OTE), their corresponding homopolymers, copolymers with thiophene and polythiophene, pyrolysis mass spectrometry technique was utilized. The results were discussed in detail considering the effects of spacer group in between ester linkages. Thermal Gravimetry Analysis was used to investigate the weight loss for polymers and monomers. Conductivities of samples were measured by four-probe technique. It was found that when the ester linkages contain hydrocarbon chains, the growth of polymer occurred through both 2 and 5 positions. On the other hand, when the ester linkages contain more rigid groups such as phenyl, steric hindrance inhibited the growth of the polymer through 2- position and polymerization proceeded via coupling of thiophene moieties mainly at 5-position yielding a polymer with lower conductivity. Though the structure of P(OTE) is inherently different than P(DATE) and P(TATE) extent of network structure is also quite low for this polymer compared to PTh. Similar thermal characterizations were recorded indicating that thermal units were not significantly affected by the presence of TATE, DATE or OTE for all copolymer samples.

Submitted by Lucas Kaique Martins Roncaselli (lucaskaiique@hotmail.com) on 2016-03-31T19:01:49Z No. of bitstreams: 1 dissertação - Fabricação e caracterização elétrica de filmes nanoestruturados de derivados do politiofeno.pdf: 2213057 bytes, checksum: 090f4d69287d8df3078f3e9849957e37 (MD5) / Approved for entry into archive by Felipe Augusto Arakaki (arakaki@reitoria.unesp.br) on 2016-04-05T13:52:15Z (GMT) No. of bitstreams: 1 roncaselli_lkm_me_prud.pdf: 2213057 bytes, checksum: 090f4d69287d8df3078f3e9849957e37 (MD5) / Made available in DSpace on 2016-04-05T13:52:15Z (GMT). No. of bitstreams: 1 roncaselli_lkm_me_prud.pdf: 2213057 bytes, checksum: 090f4d69287d8df3078f3e9849957e37 (MD5) Previous issue date: 2016-02-19 / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Neste trabalho foram utilizados derivados alquilados do politiofeno (P3ATs), sendo eles regioirregulares (RI) e regiorregulares (RR), diferenciados pela organização molecular. Esses materiais apresentam diferentes características quando fabricados usando técnicas diferentes como, a Langmuir-Blodgett (LB) e a Langmuir-Schaeffer (LS). O objetivo fica em fabricar filmes mistos com ambas as técnicas LB e LS, sendo os derivados misturados com ácido esteárico (Stearic Acid, SA), afim de verificar os diagramas de energia de acordo com a organização e condutividade de cada politiofeno. Foram depositados filmes de LB e LS de poli(3-butiltiofeno) (P3BT), poli(3-hexiltiofeno) (P3HT), poli(3-octiltiofeno) (P3OT) e de poli(3-dodectiltiofeno) (P3DDT). Os P3ATs poli(3-alquiltiofenos) foram depositados em ITO (Indium-Tin Oxide), e realizado para a caracterização desses materiais de espectroscopia UV-Visível, eletroquímicas e condutividade. Através dessas medidas foi possível estabelecer uma relação entre a organização, reversibilidade e condutividade desses materiais, possibilitando construir um diagrama de energia para esses derivados alquilados do politiofeno. / In this work we were used alkylated derivatives of polythiophene (P3ATs), and they regioirregulares (RI) andregiorregulares (RR), differentiated by molecular organization. These materials exhibit different characteristics when manufactured using different techniques such as the Langmuir-Blodgett (LB) and Langmuir-Schaeffer (LS). The objective is to manufacture mixed films with both LB and LS techniques, and derivatives mixed with stearic acid (Stearic Acid SA) in order to check the energy diagram according to the conductivity of each organization and polythiophene. LB films were deposited and LS poly(3-butylthiophene) (P3BT), poly(3-hexylthiophene) (P3HT), poly(3-octylthiophene) (P3OT) and poly(3-dodectiltiofeno) (P3DDT). The P3ATs poly(3-alquiltiofenos) were deposited on ITO (Indium-Tin Oxide), and held for characterizing these materials spectroscopy UV-Visible, electrochemical, and conductivity. Through these measures it was possible to establish a relationship between the organization, reversibility and conductivity of these materials, making it possible to build an energy diagram for these alkylated derivatives of polythiophene.

Les nanorubans de graphène (NRGs) sont des matériaux prometteurs pour l'organique électronique, à mi chemin entre polymères conjugués et nanotubes de carbone. Deux approches différentes pour la synthèse de nanorubans aromatiques sont développées et évaluées. La première est fondée sur la formation de céramidonines par cyclisation d'arylamino-anthraquinones en milieu acide. Plusieurs tétraaza-arènes incorporant deux de ces unités sont obtenus, mais l'approche s'est uniquement avérée appropriée dans le cas de courts substrats. La seconde approche repose sur la condensation d'acides aryle-acétiques avec des formylarènes ou acides aryle-glyoxyliques, suivie soit de cyclo-deshydrogénations en présence de quinone, soit de deshydrodebromation catalysée par le palladium, pour donner des arenes carboxy-substitués allongés. La méthode impliquant la quinone s'avère limitée à des substrats suffisamment réactifs tels que des thiophènes et laisse envisager des poly(arènodithiophènes) en partie rigidifiés et carboxy-substitués. La catalyse au palladium s'avère plus générale, ouvrant des perspectives d'obtention d'une grande variété de rubans aux propriétés électroniques ajustables. / Graphene nanoribbons (GNRs) are promising materials for organic electronics, as they bridge the gap betweensingle-stranded conjugated polymers and carbon nanotubes. Two different synthetic approaches to GNRs aredeveloped and evaluated. The first approach is based on the acid-promoted cyclisation of arylaminoanthraquinonesto ceramidonines. Tetraazaarenes with two ceramidonine units are obtained, but the approachis found to be appropriate only to such small systems. The second approach is based on the condensation ofarylacetic acids with arenecarboxaldehydes or arylglyoxylic acids, followed either by quinone-assistedoxidative cyclodehydrogenation or palladium-catalysed dehydrodebromination to yield carboxy-substitutedelongated arenes. The quinone-based variant is found to be limited to reactive substrates such as thiophenederivatives and offers the perspective of partially rigidified carboxy-substituted poly(arenodithiophenes). Thepalladium-based variant is found to be more general, opening the prospect of obtaining a variety of ribbontypestructures with tunable electronic properties.