I introduce the concept of modular materials and give a brief overview of their history and widespread occurrence in many areas of chemistry. I then discuss some of the many applications in which modular materials may find a use and link them to the following chapters. Chapter 1 describes the layered superatomic material Re₆Se₈Cl₂ and the induction of superconducting behavior in its single crystals through a current annealing technique. We suggest that this superconductivity arises through electron doping, as a result of dissociation of the apical Cl atoms from the clusters. Chapters 2-4 explore other types of superatomic materials and their properties, centered on the well-studied Co₆X₈ unit, where X is a chalcogen. Chapter 2 describes a Co₆Te₈-C₇₀ co-crystal that exhibits multiple phase changes with temperature, each giving rise to unique electronic, thermal, and structural properties. Chapter 3 describes a series of “solid solutions” of Co₆Se₈ and Cr₆Te₈ units. By varying the ratios of the component superatoms, transport properties of the crystals can be tuned, and unexpected behavior arises as a result of structural heterogeneity. Chapter 4 presents another study of Co₆Se₈ co-crystallized with rod-shaped C₁₄₀ fullerenes. The packing and electronic properties are found to be greatly affected by the degree of solvent inclusion. Chapters 5-6 examine another class of cluster-based materials: atomically precise gold nanoparticles. In Chapter 5 the cluster Au₂₁ is shown to self-assemble depending on the surface “hook” ligands, with corresponding differences in electronic transport. Chapter 6 discusses an interesting phase transition and thermally-induced hysteresis observed in crystals of the Au₁₀₃ cluster, also related to the surface ligand configuration. Chapters 7-8 take a different approach to modular materials, in the form of organic polymers. Using the robust, electroactive pigment molecule PDI as a common building block, we synthesize extended networks that are found to be exceptional pseudocapacitive energy storage materials. Chapter 7 introduces the honeycomb-shaped PDI-triptycene polymer, establishes its pseudocapacitive nature, and explores the role of cyclization in tuning its behavior. Chapter 8 expands upon the concept by combining PDI with hexaazatrinaphthalene to create a “contorted” network with best-in-class energy storage performance. In addition to in-depth kinetic analyses to elucidate the mechanism of storage, we fabricate two-electrode cells to demonstrate the material’s potential in real-world devices.

Two experimental methods, optical limiting and degenerate four-wave mixing, are employed to study the nonlinear optical properties of various novel fullerenes structures. Optical limiting refers to decreased transmittance of a material with increased incident light intensity. Detailed measurements of the wavelength-dependence of fullerene optical limiters have illustrated several key features of reverse saturable absorption. Most important among these is the requirement of weak but non-negligible ground state absorption. We have shown that the optical limiting performance of C₆₀ can be extended into the near infrared range by appropriate modifications of the structure such as higher cage fullerenes or derivatization of the basic C₆₀ molecule. The higher cage fullerene C₇₆ shows improved optical limiting behavior compared to C₆₀, for wavelengths higher than 650 nm, but becomes a weak limiter in the 800 nm range. C₈₄, even at high concentrations in [alpha]-chloronaphthalene, does not reach the good performance of C₆₀, but instead shows weak optical limiting in the 800 nm range. We also demonstrate that by attaching various groups to the C₆₀ molecule, we can extend the optical limiting performance in the near infrared regime. The C₆₀ derivatives studied, (C₆₀ cyclic ketone, C₆₀ secondary amine, C₆₀CHC₆H₄CO₂H, and C₆₀C₄H₄(CH₃)CH₂O₂C(CH₂)CO₂H), have a similar characteristic: the attached groups cause a symmetry-breaking of the C₆₀ sphere and, therefore, there are new allowed transitions that appear as absorption features up to 750 nm. The optical limiting measurements show that these materials, even for low input energies, have an exceptionally strong optical limiting response in the 640 to 750 nm spectral region. For wavelengths higher than 800 nm, however, they become transparent and no optical limiting is observed. Excited state absorption cross-sections obtained from analysis of the optical limiting data reveal that the C₆₀ derivatives have a maximum triplet-triplet absorption cross-section at 700 nm, which is shifted from the 750 nm value for the C₆₀ molecule. For the first time, optical limiting measurements are performed on five separate C₈₄ isomers. These intriguing results show that the optical limiting behavior is strongly dependent on the cage symmetry. It is also found that the most abundant isomer does not have the strongest optical limiting performance, but is in fact one of the weaker optical limiters of the isomers isolated so far. The endohedral metallofullerenes are a unique class of fullerene materials and consist of one or more metal atoms encapsulated inside the buckyball cage. An important characteristic of these materials is the charge-transfer from the dopant atoms to the fullerene cage, which has a high electron affinity. The charge-transfer is similar to the optical excitation in a material, but although the electrons are placed in the lowest unoccupied molecular orbital (LUMO), there are no holes produced in the highest occupied molecular orbital (HOMO). This is an important analogy, since it has been previously shown that optical excitation enhances the nonlinear optical properties of a material. The nonresonant degenerate four-wave mixing experiments performed on the endohedral metallofullerene Er₂@C₈₂, at 1064 nm, show that the third order nonlinear susceptibility value is increased by orders of magnitude relative to the empty cage fullerenes, thus, confirming the charge-transfer process from the encapsulated atoms to the fullerene cage. We obtain a value [gamma]_xyyx⁽³⁾( &#173 [omega]; [omega], [omega], &#173 [omega])= &#173 8.65 &#215 10⁻³² esu for the molecular second order hyperpolarizability, which is almost three orders of magnitude larger than the values reported in literature for an empty cage fullerene. / Ph. D.

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.

No description available.

Electric-arc vaporization of graphite rod/metal (or metal oxide) mixtures in an inert He atmosphere has been the method of choice for the production of endohedral metallofullerenes (Am@C2n). However, yields of endohedral metallofullerenes have been limited to only a few percent of the total fullerene yield, making the production and isolation of macroscopic quantities (grams) difficult. In the present study, fullerene/metal mixtures have been vaporized using a CO₂-laser beam. The sample pellets employed in the laser vaporization were prepared from empty-cage fullerenes (C60, C70, C76, C78, C84, ..• ) and small percentages, by weight, of metal or nletal oxide (La203, SC203, Y 203, Sc, Y, Er). In addition, a sample mixture of a scandium endohedral metallofullerene extract, prepared by electric-arc vaporization, was subjected to the laser. Vaporized samples were analyzed by negative-ion chemical ionization mass spectrometry and by normal phase HPLC. Inert atmospheres of helium, argon, and xenon were compared for optimization of yields of endohedral metallofullerenes, as well as for production of unique endohedral species not observed by production via electric-arc vaporization. Scandium, yttrium, and erbium endohedral metallofullerenes were synthesized by vaporization of fullerene mixtures and the appropriate metal. Optimum conditions were realized with pellet temperatures greater than or equal to 3000°C and inert gas pressures of -100 Torr. This method of CO₂ laser vaporization also served as a valuable tool to analyze the production mechanisms of fullerenes and endohedral metallofullerenes, such as production pathways (Le., C60 -> higher fullerenes -> endohedral metallofullerenes). / Master of Science

No description available.

京都大学 / 新制・課程博士 / 博士(工学) / 甲第25298号 / 工博第5257号 / 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 村田 靖次郎, 教授 近藤 輝幸, 教授 中村 正治 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

Environmental impact of fullerenes such as C60 and carbon nanotubes is of great concern due to the projection for widespread application and mass production in near future. Understanding their fate in the aqueous phase is prerequisite for accurate assessment of their ecotoxicological and human health effects upon unintended release to environment. This research addresses outstanding questions related to the behavior of fullerenes in natural and engineered water environments. Specifically, this research focuses on investigating: 1) the stability of fullerenes in the natural water, 2) interaction between fullerenes and natural organic matter (NOM), and 3) treatability of water stable fullerenes by conventional water treatment process. The experimental results suggested that NOM readily interacts with fullerenes leading to the formation of water stable fullerene suspensions. The adsorptive interaction between NOM and fullerenes was largely affected by NOM characteristics as well as water quality parameters. The fate of fullerenes in water environments was also greatly influenced by the types of fullerenes (e.g., single walled carbon nanotubes, multi-walled carbon nanotubes, and C60) and the pathway they are introduced into the aqueous phase. These water stable fullerene suspensions were found to be relatively well removed by conventional water treatment processes while the presence of NOM could negatively impact the removal efficiency. The outcomes of this study collectively imply that the dispersion of fullerenes in the natural water can occur beyond the level predicted only based on their extreme hydrophobicity and NOM plays a critical role on the fate of fullerenes both in natural and engineered water environments.

The investigation and control of the properties of carbon based materials such as fullerenes and nanotubes is a highly dynamic research field. Due to its unique properties, e.g. an almost nano-dimensional size, three-dimensional cage topology, hydrophobicity, rich redox- and photochemistry, large absorption cross section, C60 has a high potential as building block for molecular devices and biological applications. It can be functionalized, anchored to a surface and self-assembled into larger supramolecular entities, such as monolayers. Mass spectrometry and related techniques such as ion-molecule reactions, action spectroscopy and ion mobility have been used throughout this work to study fullerene based systems, ranging from hydrides, derivatives, non-covalent complexes and coordinated metal complexes. Simulations predicting structural, electronic and mechanical properties have been combined with the experimental results to assist in their analysis and interpretation. Using ion molecule reactions, the reactivity of gas phase C60 anions with methanol has been studied. Hydride formation by simple collisions in the gas phase with methanol as well as reversible dehydrogenation by infrared multiphoton activation has been demonstrated. C60 functionalization by 3-azido-3-deoxythymidine (AZT) has been performed and the charged product characterized both by collisional activation and action spectroscopy. Deprotonation has been shown to lead to rearrangements of the nucleoside analogue and to a subsequent charge transfer to the fullerene. To prevent unwanted rearrangements and side reactions, encapsulation of C60 is suggested, the host molecule acting as a steric barrier. C60 complexation by γ-cyclodextrins has been performed and the ions of the complexes characterized both by collisional activation and ion mobility. It has been demonstrated that, compared to deprotonated species, the sodiated C60:(γ-cyclodextrin)2 ions were highly compact structures. With only two small polar caps accessible to reagents, sodiated C60: (γ-cyclodextrin)2 complexes sterically protect the C60 core from unwanted side reactions. Finally, explorative work on C60 immobilization on silver colloids using surface enhanced Raman spectroscopy and on the characterization of C60 complexes with iron and manganese porphyrin is presented.

No description available.