This study involves the synthesis and structural characterization of new metal complexes of thiophene derivatives that have (potential) liquid crystalline properties. Thiophene has been selected because of its stability and versatility in lending itself to synthetic modification and hence forms links in chain structures for rod-like metallomesogens. Thiophene, when compared with 1,4-disubstituted benzene units, can change considerably the polarity, polarizability and also the geometry of the compounds, altering the types of mesophases, phase transition temperatures, dielectric constants and other properties of mesogens. The reactions of a series of 5-alkyl-2-thiophenedithiocarboxylates with nickel(II) chloride formed two types of complexes, blue mononuclear nickel(II) complexes with two terminal dithiocarboxylate ligands, [Ni(S2CTR)2] (T = 2,5-disubstituted thiophene) and violet mononuclear nickel(II) complexes with perthio- and dithiocarboxylate ligands, [Ni(S3CTR)(S2CTR)] (R = alkyl groups). The blue monomers are preferred for the shorter alkyl chains (C4 and C6), and the violet compounds for the longer chain lengths (C8, C12 and C16) in the alkylthiophene complexes. In addition to the above series, [Ni(S2CTCH3)2], was prepared in a one-pot reaction and it was possible to isolate both the blue and violet products. The thermal properties of the complexes were studied by using differential scanning calorimetry (DSC) and polarizing optical microscopy (POM). Nickel complexes of the violet type with longer alkyl chains showed liquid crystalline properties. Zinc(II) complexes analogous to nickel(II) complexes prepared similarly. A crystal structure determination of one of those complexes revealed the fusion of two monomers to give a dimeric structure with bridging sulfur atoms, [Zn2 (ƒÝ-S2CTR) 2 (S2CTR) 2]. Although an irregular melting pattern was observed, the complexes did not show any liquid crystalline properties. In an attempt to extend the study towards organometallic compounds, complexes of the type [Re(CO) 4 (S2CTR)] or [Re(CO) 4 (S2CTTR)] (T = 2,5-disubstituted thiophene, TT = 2,5-disubstituted bithiophene; R = H, CH3, C14H29) were synthesized and characterized by IR and NMR spectroscopy. Further characterization of [Re(CO) 4 (S2CTTH)] by single crystal X-ray diffraction confirmed the molecular structure of the complexes. These compounds showed sharp single melting points. Fischer-type carbene complexes of manganese(I) with octahedral coordination of the type [MnMeCp(CO) 2{C(OEtTR)}] or [MnMeCp(CO) 2{C(OEtTTR)}] (R = H, C6H13, C12H25, C16H33) were synthesized and characterized by IR, NMR and mass spectrometry. Thermal properties of the complexes were studied by using thermogravimetric analysis (TGA). All the organometallic rhenium(I) and Fischer-type carbene complexes of manganese(I) showed weight loss upon heating due to decomposition. Therefore it can be assumed that these complexes are not suitable as liquid crystals. / Thesis (PhD (Chemistry))--University of Pretoria, 2006. / Chemistry / unrestricted

Two types of Mo₂C have been investigated: polycrystalline β-Mo₂C and single crystal α-Mo₂C. The β-Mo₂C material was synthesized via a temperature-programmed method, and then characterized using x-ray diffraction (XRD), x-ray photoelectron spectroscopy (XPS), CO chemisorption, and N₂ physisorption. The catalytic activity of the β-Mo₂C was tested for cumene hydrogenation under high pressure conditions, and the effect of sulfur and oxygen poisons on cumene hydrogenation was also investigated. As a complement to the work done on polycrystalline β-Mo₂C, UHV studies of single crystal α-Mo₂C were undertaken to provide fundamental information about a well-characterized Mo₂C surface. The (0001) surface of α-Mo₂C was investigated using XPS and low energy electron diffraction (LEED). It was found that an ion-bombarded surface could be prepared as either Mo-terminated or C-terminated by choosing either low annealing temperatures (~1000 K) or high annealing temperatures (~1500 K), respectively. CO and O₂ adsorption was also studied on α-Mo₂C (0001) using thermal desorption spectroscopy (TDS), XPS, Auger electron spectroscopy (AES), and LEED. Finally, thiophene adsorption was investigated on α-Mo₂C (0001). / Ph. D.

Conjugated organic materials comprise a field of materials chemistry focused on the development of semiconducting organic plastics, popular applications of which are plastic solar cells and display technologies. One of the reasons these materials have gained so much attention is that their optical and electronic properties can be tuned through engineering at the molecular level. Thiophene, an aromatic heterocycle, is a popular building block in the synthesis of many conjugated materials, prized for both the ease in which it can be synthetically functionalized and its ability to form highly conductive and low band gap materials. The Rasmussen group has previously reported on the generation of two classes of materials, the inorganic metal thiophenedithiolenes and the fused-ring heterocycle unit thieno[3,4-b]pyrazine (TP), both of which have applications in conducting materials. In an effort to expand upon the applicability and versatility of these materials, a series of interconnected projects were performed to further tune their optical, electronic, and physical (e.g. solubility) properties. This involved synthetic molecular design, including judicious consideration of structure-function relationships, and characterization of the resulting materials. Highlights include a sterics vs. electronics consideration of the catalyzed hydrodebromination of the molecular building-block 2,3,5-tribromothiophene, variation of the coordinating metal in thiophenedithiolenes to tune the optics and electronics, and characterization of the effects of ring-fusion on TP-based terthienyl homopolymers. Additionally, a new application of the TP monomer was found, whereby it was successfully incorporated as a bridging ligand into a multi-metallic Ru(II) supramolecular assembly, which demonstrated good metal-metal communication.

É crescente o interesse, dentre os diversos tipos de dispositivos fotovoltaicos, nas células solares com corantes (dye-sensitized solar cell, DSCC). Isto é devido não só aos menores custos de produção (química molhada), mas também ao grande número de combinações orgânico/semicondutor que podem ser utilizadas, buscando as propriedades de interesse de cada dispositivo. Em uma DSSC a absorção de luz é realizada pelo material orgânico, que injeta o elétron no semicondutor para sua extração como corrente. A neutralidade da molécula é recuperada através de um eletrólito transportador de carga a partir do outro terminal. Este problema é de difícil investigação experimental, devido ao grande número de variáveis envolvidas, já que qualquer defeito ou mudança na deposição pode alterar o processo de transferência de carga. Da mesma forma, também o estudo teórico apresenta grande dificuldade, sendo necessária a adoção de modelos simplificados para o estudo, buscando um entendimento mais profundo dos processos que ocorrem durante a absorção de luz. Neste trabalho investigamos uma combinação de materiais de alta relevância, ácido retinóico sobre óxido de titânio na fase anatase, a mais importante para nanoestruturas. Realizamos uma investigação detalhada da aplicabilidade de diferentes metodologias ao problema, focalizando as características eletrônicas e óticas, e buscando evidências de transferência de carga. Para tal, analisamos modelos simples (materiais isolados, e outros sistemas diferentes de mesmas características), utilizando métodos vindos de diferentes postulações iniciais, como Hartree-Fock e Funcional da Densidade, e também partindo tanto de implementações ab initio (primeiros princípios) como de formulações semi-empíricas. Por fim, escolhida uma metodologia ideal, estudamos sistemas mais realistas de interfaces orgânico/óxido. Nossos resultados indicam a influência das dimensões nanoscópicas da matriz inorgânica nas propriedades de fotocolheita, assim como a grande importância da ligação covalente, presente na montagem quimissorvida molécula/superfície, que altera as propriedades óticas de ambos os componentes. / There is growing interest, among the many types of photovoltaic devices, in dye-sensitized solar cells (DSSC). The reasons for that are not only the lower costs of production (wet chemistry), but also the large number of organic/semiconductor combinations that can be made, depending on the properties that are interesting for each device. On a DSSC the light absorption occurs in the organic material, from which the electron is transferred to the semiconductor for current generation. The molecule regains its neutrality through an electrolyte that carries charge from the opposing terminal. The experimental investigation of this problem is very difficult, due to the large num- ber of variables involved, as any defect or change on the deposition can affect the charge transfer process. Similarly, the theoretical study is also difficult, making necessary the use of simplified models for the system to gain deeper understanding of the processes of light absorption. In this work we have studied a combination of large relevancy, retinoic acid over titanium oxide, at the anatase phase, the most important for nanostrucutres. We have thoroughly investigated the applicability of several methodologies, focusing at electronic and optical characteristics, and searching for evidences of charge transfer. For this we analyzed sim- ple models (isolated materials, and other systems that share the same characteristics), using methodologies from different starting theories, as Hartree-Fock and Density Functional The- ory, and also applying both ab initio and semi-empirical approaches. Once chosen the best methodology, we studied a more realistic system, true organic/oxide interfaces. Our results show the influence of the nanoscopic dimensions of the inorganic substrate on the properties of the photoharvest, and also the fundamental role played by the covalent bond that exists on the chemisorbed deposition of molecule/surface, that alters the optical properties of both components.

Thesis. 1977. Ph.D.--Massachusetts Institute of Technology. Dept. of Chemical Engineering. / M̲i̲c̲ṟo̲f̲i̲c̲ẖe̲ c̲o̲p̲y̲ a̲v̲a̲i̲ḻa̲ḇḻe̲ i̲ṉ A̲ṟc̲ẖi̲v̲e̲s̲ a̲ṉḏ S̲c̲i̲e̲ṉc̲e̲.̲ / Vita. / Bibliography : leaves 378-385. / by John A. Wilkens. / Ph.D.

Notre recherche se base sur la structuration des polymères conjugués qui présentent des propriétés optiques et électroniques intéressantes en raison de leur structure moléculaire intrinsèque. En effet, la structure des polymères conjugués se compose d’une alternance de simples et de doubles liaisons donnant lieu à une délocalisation des électrons le long des chaînes. Cette conjugaison est à l’origine de leurs propriétés de luminescence et de leur caractère semi-conducteur. Ces polymères sont couramment utilisés dans des dispositifs électroniques où ils jouent le rôle de composant actif. Le fonctionnement de ces dispositifs repose sur la capacité des charges à se déplacer le long des chaînes (processus intramoléculaire) et d'une chaîne à l'autre (processus intermoléculaire) et par conséquent, ces propriétés de transport dépendent de l’arrangement des chaînes polymères dans le solide, qui lui-même découle des interactions supramoléculaires. Il est donc impératif de maîtriser ces interactions et d’étudier l’influence qu’elles ont sur les performances de tels dispositifs électroniques. C’est précisément sur ce point que porte notre travail : étudier et contrôler la formation de nanostructures en termes de dimensions, de forme et de localisation, en appliquant une contrainte physique extérieure à un film de polymère conjugué. Le polymère conjugué sur lequel notre étude se base principalement est le poly(3-hexylthiophène), P3HT. Ce polymère est semi-cristallin et possède une mobilité de charge élevée (0.18 cm2/V.s), ce qui en fait un très bon candidat en tant que composant actif dans les transistors à effet de champ. Nous avons, dans le cadre de notre recherche, étudié la structuration de films minces de P3HT, réalisée par l’application de contraintes physiques extérieures. L’utilisation d’une pointe de microscope à force atomique travaillant en mode contact permet de déformer plastiquement la surface polymère en créant des structures périodiques en surface des films mais elle permet, en outre, d’orienter les chaînes polymères dans la direction de passage de la pointe. Différents paramètres expérimentaux ont été étudiées comme par exemple, la résolution choisie pendant l’expérience, le nombre de passage effectués par la pointe ou encore l’angle avec lequel la pointe structure le film polymère. Nous avons également démontré que cette technique, appliquée au canal polymère d’un transistor à effet de champ, permet d’améliorer les propriétés électriques du P3HT et par conséquent, d’augmenter les performances du dispositif électronique. Nous avons utilisé une autre méthode, dite de « lithographie douce », afin de structurer le P3HT. Cette technique présente l’avantage de « façonner » le polymère lorsqu’il se trouve en solution et ne nécessite donc pas la formation préalable d’un film. Elle consiste à déposer une goutte de solution polymère sur un substrat, à l’entrée de canaux micrométriques de PDMS; l’écoulement de la solution polymère, qui se fait par capillarité dans les canaux, est donc confiné. Le solvant va ensuite s’évaporer et il reste alors, sur le substrat, un dépôt polymère qui est la réplique négative des canaux de PDMS. L’analyse du dépôt polymère formé grâce à cette méthode révèle, comme c’était le cas pour la technique précédente, une orientation des chaînes polymères au sein des canaux. Dans la dernière partie de ce travail, nous avons étudié le dopage de films fibrillaires de P3HT. L'étude de la morphologie des films dopés montre que la structure fibrillaire est conservée, avec une légère augmentation de la largeur des fibrilles. Cette augmentation résulte d'un déplacement des chaînes polymères les unes par rapport aux autres dans l'axe du squelette conjugué afin de laisser des espaces vacants pour accueillir les contre-ions dans le réseau polymère. Les mesures électriques des films dopés montrent un accroissement très important de la conductivité du polymère. On observe une augmentation de six ordres de grandeur entre les conductivités d'un film neutre et dopé.

Dicationic diamidines synthesized in the Boykin group a have shown broad range of activity against a wide variety of microbial pathogens such as Cryptosporidium parvum, Leishmania donovani, Plasmodium falciparum, Trypanosoma burcei, and Trichomonas vaginalis. Thiophene based dicationic diamidines have been especially impressive versus Trichomoniasis, and several species of the leishmania parasite. The best compound in vitro against leishmania was 2,5-bis-(4-amidophenyl)thiophene [DB 351]. In an attempt to improve upon antileishmanial activity, several analogs of DB 351 have been synthesized. Previously the central heterocyclic ring has been changed (furan, pyrrole, etc.), and the phenyl has been substituted with a pyridine ring, however, in the thiophene series, the 3 and 4 position of the central thiophene ring has remained unmodified. By modifying the 3 and 4 position of the thiophene ring, and taking advantage of the substituent effect, the pharmacodynamic and distribution properties of DB 351 will altered; hopefully leading to more potent antileishmanial compounds.

Dicationic diamidines synthesized in the Boykin group a have shown broad range of activity against a wide variety of microbial pathogens such as Cryptosporidium parvum, Leishmania donovani, Plasmodium falciparum, Trypanosoma burcei, and Trichomonas vaginalis. Thiophene based dicationic diamidines have been especially impressive versus Trichomoniasis, and several species of the leishmania parasite. The best compound in vitro against leishmania was 2,5-bis-(4-amidophenyl)thiophene [DB 351]. In an attempt to improve upon antileishmanial activity, several analogs of DB 351 have been synthesized. Previously the central heterocyclic ring has been changed (furan, pyrrole, etc.), and the phenyl has been substituted with a pyridine ring, however, in the thiophene series, the 3 and 4 position of the central thiophene ring has remained unmodified. By modifying the 3 and 4 position of the thiophene ring, and taking advantage of the substituent effect, the pharmacodynamic and distribution properties of DB 351 will altered; hopefully leading to more potent antileishmanial compounds.

3-(o-(Methylthio)phenyl)-1-phenylprop-2-en-1-one (48) ¡B1-(o-(methylthio)-phenyl)-3-phenylprop-2-en-1-one (49) and 1-(o-(methylthio)phenyl)-3-phenylprop-2-yn-1-one (50) had been studied by means of pyrolysis and photolysis. Under pyrolytic conditions, compound 48 gave phenanthrene (2) as the major product. Both compounds 49 and 50 gave thioflavone (53) as the major product. Under photolytic conditions, compounds 48-50 gave the expected products 2-benzoylbenzo[b]thiophene (51)¡B 2-benzylidenebenzo[b]thiophen-3-one (52) and thioflavone (53), respectively.

Treatment of 1-(methylsulfinyl)-2-(phenylethynyl)benzene with 10 mol % of mercury dichloride and 1 equivalent of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone in refluxing benzene gave benzo[b]thiophene in good yields. This method tolerated various functional groups in phenylethynyl moiety, including electron donating groups and electron withdrawing groups. Useing 1-(benzylsulfinyl)-2-(phenylethynyl)benzene as reaction substrate increased the yields of benzo[b]thiophene derivatives. Isotope effect showed that this cyclization reaction belong to Pummerer type cyclization reaction.