京都大学 / 0048 / 新制・課程博士 / 博士(理学) / 甲第20951号 / 理博第4403号 / 新制||理||1632(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 大須賀 篤弘, 教授 丸岡 啓二, 教授 依光 英樹 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

The field of single-molecule magnetism studies nanoscopic objects which exhibit superparamagnetic behavior below a certain temperature. The molecular magnet consists of one or several magnetic metal ions and the surrounding ligands that form the desired environment. Manganese was the first from 3d metals to show a delayed relaxation of magnetization and magnetic hysteresis in Mn12AC molecule in 1993. Later 4f elements were found to be even better candidates for single-molecule magnets. Endohedral fullerenes show a wide potential in encapsulating 4f elements. Not only fullerenes with one or several 4f-block metal ions can be obtained but also various clusterfullerenes comprising several positively charged metal ions and up to several negatively charged ions like N-3, S-2, etc. Importantly not only 4f elements can form clusters inside the fullerene cage but also non-magnetic metals like Y and Sc. This allows to vary the number of magnetic ion in the cluster retaining almost similar structure. This thesis reports magnetic studies of various Dy endohedral fullerenes: DySc2N@C80 and Dy2ScN@C80, which are the pioneer endohedral fullerene single-molecule magnets. For DySc2N@C80, the intriguing process of quantum tunneling of magnetization was studied in detail for powder and single-crystal samples with different dilution methods. For Dy2ScN@C80, the coupling between two Dy ion is of the main interest. Magnetic studies of this compound revealed: that the quantum tunneling process is effectively suppressed due to exchange interactions in the cluster; and a large anisotropy barrier of 1735±21 K. Dy2S@C82-Cs, -C3v, Dy2S@C72-Cs, Dy2C2@C82-Cs fullerenes were studied in order to obtain a deeper understanding of the coupling of magnetic elements inside the cage. The investigation of a fullerene family with a similar cluster in cages of different symmetry and different clusters in the same fullerene cage allowed to separate the influence of the cluster composition and the cage structure on magnetic properties of endohedral metallofullerene single-molecule magnets. The cage structure was found to have a dominant influence. Dy2@C80(CH2Ph) is a special endohedral metallofullerene with a single-electron Dy Dy bond. It represents the ultimate case of magnetic coupling and exhibits a record-high blocking temperature (21.9 K) among di-metal single-molecule magnets. The comparison of obtained results allowed to understand how the quantum tunneling is influenced by of both intramolecular interactions and magnetic coupling inside the fullerene cage. Also, Dy2@C80(CH2Ph) endohedral metallofullerene with a single-electron lanthanide-lanthanide bond opens the new class of tunable single-molecule magnets, with outstanding magnetic properties.

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The state-of-the-art organic solar cells (OSC) use bulk heterojunction (BHJ) blend architecture in the photo-active layer. The BHJ is formed by finely mixing polymer donor and small molecule acceptor, which was predominantly fullerene derivatives until the last five years. However, the emergence of non-fullerene acceptor (NFA) materials has been the viable alternative to overcome high synthetic costs, limited optical absorption, and poor bandgap tunability of fullerene-based acceptors. These unique properties of NFA has resulted in a rapid improvement of OSC efficiency and opened doors for wide variety of applications including building integrated photovoltaics, green houses and agrivoltaics. Despite these advantages, the shorter device lifetime under light and heat is a major concern for their commercialization. This dissertation is focused on improving poor photo- and thermal stability of high efficiency OSC based on the widely used NFA, ITIC and Y-series derivatives. The light-induced changes in the acceptor molecular structure and the active layer nanostructure results in the photo-induced traps in photo-aged devices. The selective addition of third component to the active layer impedes the changes in the active layer nanostructure and suppress trap formation. Under constant thermal stress, the growth of acceptor crystals results increases the trap-assisted recombination in thermally aged devices. Similar to photo-stability the selective addition of third or more component/s arrests the crystal growth by minimizing the Gibbs free energy. The results suggest that the fabricated hexanary and ternary OSC display a superior thermal stability than the respective binary devices. In addition, the hexanary devices displayed thickness independent thermal stability, which is essential for the active layer thermal stability printed via high throughput techniques.

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Endohedral metallofullerenes (EMF) have attracted increasing attention during past decades for their potential applications in the fields of biomedicine and nanomaterials. Trimetallic nitride template endohedral metallofullerenes (TNT EMFs) are some of the most promising fullerene-based materials (e.g., as MRI and X-ray contrast agents) because of their high yields compared to classic endohedral metallofullerenes. This dissertation addresses the chemical reactivity and regioselectivity of TNT EMFs. Based on the extraordinarily high stability of TNT EMFs relative to empty cage fullerenes and classic endohedral metallofullerenes, macroscopic quantities of high purity TNT EMFs were obtained directly from crude soot in a single facile step by using a cyclopentadiene-functionalized resin to trap the more reactive species via Diels-Alder reactions, allowing the TNT EMFs to pass through. We also developed a support-free chemical separation method of TNT EMFs from Sc- and Lu-based soot extract that makes use of the differing solubilities of unreacted TNT EMFs versus 9-methylanthracene-derivatized empty cage fullerenes. The exohedral functionalization of metallofullerenes can fine-tune their chemical and physical properties. The first N-methylpyrrolidino derivatives of TNT EMFs (Ih Sc3N@C80 and Ih Er3N@C80) were synthesized via 1,3-dipolar cycloaddition of N-methylazomethine ylides (Prato reaction). The demonstration of planar symmetry in the N-methylpyrrolidino derivatives by 13C NMR spectroscopy suggested that the reaction exclusively took place at the 5,6-ring junction. However, both 5,6-ring and 6,6 ring junction adducts were obtained when Ih Sc3N@C80 reacted with N-triphenylmethyl-5-oxazolidinone, as characterized by NMR spectroscopy and X-ray crystallography. The kinetically favored 6,6-ring junction adduct was converted to the thermodynamic product, the 5,6-ring junction adduct, upon thermal equilibration. The synthesis of pyrrolidino derivatives was also extended to two other Sc-based TNT EMFs, D5h Sc3N@C80 and Sc3N@C78. The reactivity and regioselectivity of D5h Sc3N@C80 and Sc3N@C78 were demonstrated by NMR spectroscopy, X-ray crystallography and theoretical calculations. Another type of reaction, the Bingel-Hirsch cyclopropanation was carried out with D3h Sc3N@C78 for the first time, yielding a single Cs-symmetric monoadduct and a dominant C2v-symmetric diadduct for the first time. The symmetric diadduct clearly demonstrates the remarkable regioselectivity control exerted by the encapsulated Sc3N cluster. We employed a LUMO electron density surface computational approach to predict multiadduct docking sites on the ellipsoidal fullerene cage surface. We also successfully synthesized the first derivative of a non-IPR fullerene, the diethyl malonate derivative of Sc3N@C68 by a Bingel-Hirsch reaction. The reactivity and regioselectivity of Sc3N@C68 were investigated by NMR spectroscopy and theoretical calculations. / Ph. D.

Since the discovery three decades ago, fullerenes as well as metallofullerenes have been extensively investigated. However, almost all known fullerenes follow the classical definition, that is, classic fullerenes are comprised of only pentagons and hexagons. Nowadays, more and more evidence, from both theoretical and experimental studies, suggests that non-classical fullerenes, especially heptagon-containing fullerenes, are important as intermediates in fullerene formation mechanisms. To obtain fundamental understandings of fullerenes and their formation mechanisms, new systematic studies should be undertaken. Although necessary tools, such as isomer generating programs, have been developed for classical fullerenes, none of them are able to solve problems related to non-classical fullerenes. In this thesis, existing theories and algorithms of classical fullerenes are generalized to accommodate non-classical fullerenes. A new program based on these generalized principles is provided for generating non-classical isomers. Along with this program, other tools are also attached for accelerating future investigations of non-classical fullerenes. In addition, research to date is also reviewed. / Master of Science

The discovery that negatively charged aggregates of C60 fullerene are stable in aqueous environments has elicited concerns regarding the potential environmental and health effects of these aggregates. Although many previous studies have used aggregates synthesized using intermediate organic solvents, this work primarily employed an aggregate production method that more closely emulates the fate of C60 upon accidental release into the environment — extended mixing in water. The aggregates formed via this method (aqu/nC60) differ from those produced using the more common solvent exchange methods. The aqu/nC60 aggregates are heterogeneous in size (20 nm and larger) and shape (angular to round), negatively charged, and crystalline in structure — exhibiting a face centered cubic (fcc) system. Solution characteristics such as aqu/nC60 aggregate size and concentration were found to be dependant upon preparation variables such as stirring time, initial C60 concentration, and initial particle size. Additional experiments indicate that aggregate charge, structure, and stability are highly dependant upon the identity of co-solutes (NaCl, CaCl2, sodium citrate) and their concentrations. Citrate concentrations greater than 0.5 mM resulted in the formation of very small (< 20 nm) spherical aqu/nC60 particles. At moderate citrate concentrations (~ 1 mM) a more negative surface charge was observed, which may be an indication of increased nC60 stability. In contrast, high concentrations of monovalent and divalent electrolytes result in aggregation and sedimentation of nC60 out of solution. Our research describes the effect that solution composition has on aggregate formation and stability, and suggests that C60 fate and transport will be a function of solution composition. / Master of Science

Despite the rapid growth in nanotechnology, very little is known about the unintended health or environmental effects of manufactured nanomaterials. The development of nanotechnology risk assessments and regulations requires quantitative information on the potential for exposure to nanomaterials. In addition, to facilitate life-cycle assessments and inhalation toxicology studies, robust methods are needed to generate aerosolized engineered nanoparticles. We conducted a set of field studies to measure the fine particle mass concentrations (PM2.5) as well as nanoparticle number concentrations and size distributions in two nanomaterial manufacturing facilities. Measurements were performed near the reactor, in the breathing zone, and at a background site. Increases in PM2.5 and particle number concentrations were associated with physical handling of nanomaterials. The highest PM2.5 concentration observed was 2700 ug m-3 during sweeping of the reactor in the commercial plant. In most cases, an increase in the number of sub-100 nm particles accounted for the increase in total number concentrations. The results of this research can be used to develop guidelines for workplace regulations to minimize workers' exposure to nanoparticles. Furthermore, we used an atomizer to aerosolize C60 aggregates from a fullerene-water suspension. Measurement of particle size distributions and number concentrations showed that increasing the initial fullerene concentration resulted in increased number of aerosolized particles, while the average size of particles remained relatively constant. To return the aerosolized fullerenes into water, we passed the aerosol sample through an impinger. Reducing the flow rate through the impinger resulted in an increase in the collection efficiency of airborne nanoparticles. / Master of Science