La synthèse de graphène par approche « bottom-up » fait l’objet de nombreux travaux de recherche ayant pour but de contrôler les propriétés électroniques et optiques de ce matériau par la fabrication de nanostructures avec une précision atomique. D’autre part, le contrôle de dopant dans le graphène permettant d’en moduler les propriétés suscite un grand intérêt et dans ce contexte l’utilisation de porphyrines avec un taux d’azote contrôlé est attrayante. Par leurs ressemblances structurelles, les porphyrines π-étendues peuvent être considérées comme des nanoparticules de graphène dopées à l’azote (GQDs) présentant de fortes propriétés infrarouge tandis que les briques de construction à base de porphyrines peuvent être utilisées pour la synthèse sur surface de deux type de nanoarchitectures de graphene appélées nanorubans (GNRs) et nanomèches (GNMs). Cette thèse a pour objectif de développer la synthèse de porphyrines à base d’anthracenes et de les utiliser comme précurseurs pour la fabrication de nanostructures. La première partie de cette thèse est dédiée à la synthèse organique de différentes anthracenylporphyrines et à l’étude de leurs assemblages sur surface dans la chambre d’un microscope à effet tunnel. La seconde partie est dédiée à l’étude de formation de porphyrines π-étendues via une méthode pyrolyse flash pouvant activer thermiquement des réactions de couplage par déhydrogenation entre des hydrocarbures aromatiques polyycliques (PAHs) et des porphyrines. La dernière partie est dédiée à la modification post synthétique d’une tetrabromoanthracenylporphyrine par addition de PAHs via la réaction de couplage de Suzuki-Miyaura et à la caractérisation des propriétés optiques de ces porphyrines nouvellement formées. / The synthesis of graphene via bottom-up approach is a hot topic of research that aims to control the electronic and optical properties of this material by the fabrication of atomically precised nanostructures. Moreover, the control of dopant in graphene is of great interest to modulate the properties of the material. In this context, the contribution of porphyrins with a controlled content of nitrogen is attractive in this context. Because of structural similarities with graphene quantum dots (GQDs), π-extented porphyrins can be regarded as nitrogen-doped GQD with promising NIR properties. Porphyrins are convenient building blocks for the synthesis on surface of nanoarchitectures of graphene called nitrogen-doped Graphene Nanoribbons (GNRs) and Graphene NanoMeshes (GNMs). This thesis aims to develop the synthesis of symmetrical and robust porphyrins with anthracenes and to use them as precursors for the fabrication of nanostructures. The first part of this thesis is dedicated to the organic synthesis of variety of anthracenylporphyrins and the study of their assemblies on surface in a chamber of a Scanning Tunneling Microscope. The second part is dedicated to the study of formation of π-extended porphyrins via a method of flash pyrolysis able to thermally activate dehydrogenative coupling reactions between Polycyclic Aromatic Hydrocarbons (PAHs) and porphyrins. The last part is dedicated to the post synthetic modification of a tetrabromoanthracenylporphyrin with additional PAHs via Suzuki-Miyaura coupling and the characterization of the optical properties of the resulting porphyrins.

京都大学 / 0048 / 新制・課程博士 / 博士(理学) / 甲第18823号 / 理博第4081号 / 新制||理||1587(附属図書館) / 31774 / 京都大学大学院理学研究科化学専攻 / (主査)教授 大須賀 篤弘, 教授 時任 宣博, 教授 丸岡 啓二 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第20387号 / 工博第4324号 / 新制||工||1670(附属図書館) / 京都大学大学院工学研究科材料化学専攻 / (主査)教授 松原 誠二郎, 教授 大江 浩一, 教授 中尾 佳亮 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第21117号 / 工博第4481号 / 新制||工||1696(附属図書館) / 京都大学大学院工学研究科物質エネルギー化学専攻 / (主査)教授 辻 康之, 教授 大江 浩一, 教授 村田 靖次郎 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

No description available.

No description available.

No description available.

No description available.

京都大学 / 新制・課程博士 / 博士(理学) / 甲第23729号 / 理博第4819号 / 新制||理||1689(附属図書館) / 京都大学大学院理学研究科化学専攻 / (主査)教授 長谷川 健, 教授 若宮 淳志, 教授 渡邊 一也 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

Três novas supermoléculas, aqui designadas por ZnTCP4+, MnTCP5+ e CoTCP5+, foram obtidas pela coordenação de quatro acetatos trinucleares assimétricos de rutênio, [Ru3O(CH3CO2)6(py)2(CH3OH)]+, aos resíduos piridínicos de meso-tetra(4-piridil)porfirinato de ZnII, MnIII e CoIII, respectivamente (ZnTPyP, MnTPyP e CoTPyP). A caracterização destas supermoléculas foi efetuada por espectroscopia de ressonância magnética nuclear e espectroscopia eletrônica. O comportamento eletroquímico foi investigado por voltametria cíclica e espectroeletroquímica. Os efeitos dos acetatos trinucleares periféricos sobre a reatividade do núcleo porfirínico foram analisados: (i) para ZnTCP4+, além da supressão da luminescência, verificou-se que as constantes de coordenação axial determinadas em diclorometano para piridina e imidazol, quando comparadas às respectivas constantes de ZnTPyP e de meso-tetra(fenil)porfirinato de zinco, indicaram um aumento significativo da acidez de Lewis do íon Zn2+; (ii) MnTCP5+ revelou-se um catalisador mais seletivo que MnTPyP na oxidação de ciclohexano em fase homogênea, utilizando-se iodosilbenzeno como doador de oxigênio; (iii) os eletrodos modificados por filmes de CoTCP5+ apresentaram uma eficiente atividade catalítica na redução tetra-eletrônica de dioxigênio a água, comportamento que contrasta com o descrito na literatura para filmes de CoTPyP. A redução tetra-eletrônica de dioxigênio catalisada pelos filmes de CoTCP5+ foi confirmada por voltametria cíclica, voltametria de eletrodo disco rotatório e voltametria de eletrodo de anel e disco rotatórios. / Three novel supermolecules designated as ZnTCP4+, MnTCP5+, and CoTCP5+ were obtained by coordination of four assymetric trinuclear ruthenium acetate species, [Ru3O(CH3CO2)6(py)2(CH3OH)]+ to pyridine residues of ZnII -, MnIII -, and CoIIITPyP, respectively (TPyP = meso-tetra(4-pyridil)porphyrinate). These new compounds were characterized by nuclear magnetic resonance spectroscopy and electronic spectroscopy. The electrochemical behavior was investigated by cyclic voltammetry, and spectroelectrochemistry. The influence of the peripheral trinuclear acetate on the porphyrin core reactivity was assayed: (i) for ZnTCP4+, besides the luminescence quenching, the calculated equilibrium constants for axial coordination of pyridine and imidazole in dichloromethane demonstrated a significant increase in the Zn2+ Lewis acidity in comparison with the respective constants from ZnTPyP and zinc meso-tetra(phenyl)porphyrinate; (ii) MnTCP5+ exhibited improved selectivity as catalyst for ciclohexane oxidation (homogeneous phase) in comparison with MnTPyP using iodosylbenzene as oxygen donor; (iii) modified electrodes by CoTCP5+ films showed an outstanding catalytic activity in the tetraelectronic reduction of dioxygen to water, in contrast with CoTPyP films described in the literature; the dioxygen tetraelectronic reduction was confirmed by cyclic voltammetry, rotating disk electrode voltammetry, and rotating ring and disk electrode voltammetry.