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京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第19734号 / 工博第4189号 / 新制||工||1646(附属図書館) / 32770 / 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 村田 靖次郎, 教授 杉野目 道紀 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第21116号 / 工博第4480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 松田 建児 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

No description available.

A large variety of diferrocenyl compounds bridged by an organic wire fragment in a generic form of -CH=CH-X-CH=CH- were first synthesized, in which the X unit is a functional group/atom. These compounds were studied by structural analysis, electrochemistry, intervalence NIR absorption and other spectroscopic techniques. The results indicated that metal-ligand redox matching is most essential in facilitating long-range electron transfer in the mixed-valence complexes. A series of doubly-bridged diferrocenyl compounds and wire-linked triferrocenes were also synthesized and studied. All doubly-bridged diferrocenyl compounds demonstrated nearly doubled electronic coupling in comparison to their singly-bridged analogues. Thus the use of parallel wires in such systems represents a facile approach to improve communication in molecular electronics. For triferrocenes linked by symmetric wires, the electronic interaction between the redox-active centers was rather dynamic when the bridging component was short or the charge was delocalized among the ligand and metal centers. For triferrocenes bridged by asymmetric wires, depending on the direction of the polar linking chain, the central ferrocene becomes a molecular switch, turning on or off the communication between the two end ferrocenes. Finally, to eliminate the metal-ligand orbital mixing problem, we also bound the wires with two redox-active styrylpyrrole termini, for which the molecules are purely organic. It was found that when the ð-conjugation was maintained, the oligomers were fully delocalized systems.

Ce travail est consacré à la synthèse et la caractérisation des commutateurs et des fils moléculaires incorporant l'unité et le ruthénium organométalliques fractions photochromiques. La première partie traite de lanthanides complexe Yb combiné avec l'unité et le ruthénium acétylure fractions photochromiques afin de moduler la luminescence avec l'aide de redox et de stimuli lumineux. Dans la deuxième partie explique la combinaison d'unités DTE photochromiques avec des fragments acétylures de ruthénium pour fixer sur la surface de nanoparticules métalliques afin d'affiner leur résonance plasmonique grâce à la modification de l'environnement de surface en utilisant la lumière et redox stimuli. La troisième partie décrit la préparation de complexes de lanthanides combinés avec une unité photochromique spiropyranne pour commuter les propriétés SMM des complexes via photoisomérisation de l'unité spiropyranne. Dans la dernière partie, nous présentons la synthèse de Oligo (phénylène éthylène) Les fils moléculaires avec différents noyaux centraux afin d'obtenir une variété de fil avec différents niveaux d'énergie HOMO-LUMO pour vérifier l'effet de l'épinglage. / This work is devoted to the synthesis and characterization of novel molecular switches and wires incorporating photochromic unit and ruthenium organometallic moieties. The first part deals with lanthanide Yb complex combined with photochromic unit and ruthenium acetylide moieties in order to modulate the luminescence with the help of redox and light stimuli. In the second part explained the combination of photochromic DTE units with ruthenium acetylide moieties to attach on the surface of metal nanoparticles in order to tune their plasmonic resonance through the surface environment modification by using light and redox stimuli. The third part describes the preparation of lanthanide complexes combined with a spiropyran photochromic unit in order to switch the SMM properties of the complexes via photoisomerization of the spiropyran unit. In the last part, we report the synthesis of Oligo(phenylene ethylene) molecular wires with different central cores in order to obtain various wire with different HOMO-LUMO energy levels to check the effect of pinning.

No description available.

This dissertation attempts to understand how energy transfer in a molecular wire and a spherical organic assembly are affected by molecular structure. The molecular wire is a DNA-hybrid structure composed of a strand of thymine bases appended by a cyanine dye. Hydrogen bonded to each base is a naphthalene-derivative molecule. Using time-integrated photoluminescence and time-correlated single photon counting measurements, energy transfer from the naphthalene donors to the cyanine acceptors was confirmed, and its dependence on temperature and DNA-template length investigated. Donor-thymine bonding was disrupted at temperatures above about 25 degrees Celcius resulting in poor donor template decoration and low rates of energy transfer. Increasing numbers of donors attach to the scaffold, forming an orderly array, as the template length increases due to the stabilising effects of the donor-donor pi-stacking interactions. Conversely, modelled energy transfer rates fall as the scaffold length increases because of the longer donor-acceptor distances involved. Therefore, the energy transfer rate was greatest for a template built from 30 thymines. The spherical organic assemblies (nanoparticles) are formed by fast injection of a small volume of molecularly dissolved fluorene-derivative amphiphilic molecules into a polar solvent. The amphiphilic molecules contained either a naphthalene (donor) or a benzothiadiazole (acceptor) core. The donor-acceptor mixed nanoparticles resemble an amorphous polymer film and were modelled as such using the Foerster resonance energy transfer theory. The Foerster radii extracted from the measurements depends intricately on the donor-acceptor spectral overlap and distance. The latter effect was controlled by the stacking interactions between the molecules. Altering the morphology of the structural units is the key to optimising energy transfer in molecular structures. To achieve efficient organic molecule-based devices, the importance of this property needs to be fully appreciated and effectively exploited.