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Song, Xu. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2007. / Includes bibliographical references (leaves 92-96). / Abstracts in English and Chinese. / Table of Contents --- p.i / Acknowledgements --- p.iii / Abbreviations --- p.iv / Abstract --- p.v / Chapter Part I --- Carbon-Carbon Bonds Activation (CCA) of Ketones by Iridium(III) Porphyrins / Chapter Chapter 1 --- General Introduction / Chapter 1.1 --- Carbon-Carbon Bonds Activation by Transition Metals --- p.1 / Chapter 1.2 --- Thermodynamic and Kinetic Considerations in CCA --- p.1 / Chapter 1.3 --- C-C Bonds Activation by Low Valent Transition Metal Complexes --- p.3 / Chapter 1.3.1 --- CCA in Strained System --- p.3 / Chapter 1.3.2 --- CCA Driven by Aromatization --- p.6 / Chapter 1.3.3 --- Chelation Assisted CCA --- p.8 / Chapter 1.4 --- C-C Bonds Activation by High Valent Transition Metal Complexes --- p.11 / Chapter 1.5 --- Previous Mechanistic Studies on CCA by High Valent Transition Metal Complexes --- p.14 / Chapter 1.6 --- Objective of the Work --- p.16 / Chapter Chapter 2 --- Carbon-Carbon Bonds Activation (CCA) of Ketones by Iridium(III) Porphyrins / Chapter 2.1 --- Introduction --- p.17 / Chapter 2.2 --- CCA of Aromatic Ketones with Iridium(III) Porphyrins --- p.17 / Chapter 2.2.1 --- CCA of Aromatic Ketones with Ir(III) Porphyrin Chloride --- p.17 / Chapter 2.2.2 --- CCA of Aromatic Ketones with Ir(III) Porphyrin Methyl --- p.20 / Chapter 2.2.3 --- Steric Effect on CCA with Ir(III) Porphyrins --- p.21 / Chapter 2.3 --- CCA of Aliphatic Ketones with Iridium(III) Porphyrins --- p.21 / Chapter 2.3.1 --- CCA of Unstrained Aliphatic Ketones with Ir(III) Porphyrins --- p.21 / Chapter 2.3.2 --- CCA of Cyclic Aliphatic Ketones with Ir(III) Porphyrins --- p.22 / Chapter 2.4 --- Summary --- p.23 / Chapter Chapter 3 --- Preliminary Mechanistic Studies of Carbon-Carbon Bonds Activation (CCA) / Chapter 3.1 --- Proposed Mechanism of CCA with Ir(III) Porphyrin Chloride --- p.24 / Chapter 3.2 --- Proposed Mechanism of CCA with Ir(III) Porphyrin Methyl --- p.27 / Chapter 3.3 --- Determination of CCA co-product in situ --- p.30 / Chapter 3.4 --- Summary --- p.31 / Experimental Section --- p.33 / References --- p.44 / List of Spectra I --- p.48 / Chapter Part II --- Supramolecular Chemistry of C6o with Ir(III) Porphyrin Methyl / Chapter Chapter 1 --- General Introduction / Chapter 1.1 --- Supramolecular Interactions --- p.62 / Chapter 1.2 --- Introduction of C6o --- p.67 / Chapter 1.3 --- Supramolecular Interactions between C6o and Metalloporphyrins --- p.70 / Chapter 1.3.1 --- Discovery of Supramolecular Interactions between C6o And Metalloporphyrins --- p.70 / Chapter 1.3.2 --- Development of C6o-Metalloporphyrin Supramolecular Structure and Application --- p.71 / Chapter 1.3.3 --- Investigation on C6o-Metalloporphyrin Bonding Nature --- p.73 / Chapter 1.4 --- Objective of the Work --- p.76 / Chapter Chapter 2 --- Supramolecular Interaction between C60 and Ir(III) Porphyrin Methyl / Chapter 2.1 --- Synthesis of C60-Ir(ttp)Me Complexes --- p.77 / Chapter 2.2 --- X-ray Structure Analysis of C60-Ir(ttp)Me Complexes --- p.78 / Chapter 2.3 --- 1H NMR Analysis of C60-Ir(ttp)Me Complexes --- p.83 / Chapter 2.4 --- 13C NMR Analysis of C60-Ir(ttp)Me Complexes --- p.84 / Chapter 2.5 --- Binding Constant of C60-Ir(ttp)Me Complexes Using UV-Vis Analysis --- p.85 / Chapter 2.6 --- Summary --- p.87 / Experimental Section --- p.88 / References --- p.92 / Appendix --- p.97 / List of Spectra II --- p.101 / Reprint of OM Paper --- p.112 / Supporting Information for Organometallics Paper --- p.118

Les travaux développés au cours de cette thèse comprennent le dessin, modélisation, synthèse et caractérisation de nouveaux matériaux polymérisés à base de fullèrene. Dans le cadre d'une utilisation au sein de cellules photovoltaïques, ces matériaux doivent démontrer propriétés telles que solubilité dans des solvants organiques, miscibilité avec le polymère absorbeur de lumière et stabilité morphologique supérieures à celles rencontrées pour les matériaux déjà en utilisation, tels les (bis-)PC60BM et les dérivés d'indene-C60. Six routes de synthèse différentes ont été étudiées et les propriétés électroniques (énergie de LUMO, électroaffinité, électrophylicité, énergies de réorganisation, intégrale de transfert et mobilité électronique) qui en résultent ont été déterminées par des méthodologies de modélisation numérique. Parmi ces composés modèles, la route dite ATRAP a été retenue pour être synthétisée vue qu'elle a été peu étudiée dans la littérature. Les propriétés physico-chimiques de ces composés synthétisés avec des différentes chaînes latérales ont été déterminées par plusieurs techniques et leur application dans des couches minces au sein des dispositifs photovoltaïques a été mise en place. Quand utilisés comme additifs, ces matériaux présentent un potentiel de stabilisation de la couche de P3HT/PC60BM, vu que la performance des cellules qui l'ont est très peu affectée. Le comportement de ces couches sous traitement thermique a montré un effet de non-stabilisation dont le mécanisme a été, lui aussi, étudié par diverses techniques expérimentales. Finalement, un mécanisme de dépolymérisation induit par lumière et/ou chaleur a été proposé. Selon ceci, la cassure de la liaison chimique entre le monomère et le fullèrene est responsable pour la création des défauts, dépolymérisation, cross-linkings et réarrangement irréversible de la couche mince. Cette cassure peut être soit thermiquement activée, soit par l'état triplet du monomère qui déstabilise cette même liaison. Outre que l'étude de ces composés, la stabilisation de l'interface organique-inorganique en dispositifs photovoltaïques, la stabilisation de la chaîne latérale des polymères conjugués et la relation entre affinité avec oxygène moléculaire et la géométrie de la molécule en question ont été adressées. Ces études parallèles ont été achevées par la proposition de nouveaux matériaux hybrides du type donneur-accepteur dérivés de hexabenzocoronene capables de s'empiler dans des structures similaires à des cristaux liquides discotiques. À partir des connaissances acquises au cours de ce document, deux composés ont été proposés et leurs propriétés électroniques montrent qu'il est possible de dessiner des matériaux qui peuvent être, à la fois, stables et efficaces pour être utilisés dans le domaine du photovoltaïque organique. / The work developed during this thesis include the design, modeling, synthesis and characterization of new polymeric materials based on fullerenes. In the optics of a use within photovoltaic cells, these materials have to present particular properties, among which a good solubility in organic solvents, a good miscibility with the light-absorber polymer as well as a morphological stability superior to those currently used materials, such as (bis-)PC60BM and the derivatives of indene-C60. Six different synthetic routes were studied and the electronic properties (LUMO orbital energy, electroaffinity, electrophilicity, reorganization energy, transfer integral and electron mobility) risen were determined by molecular modeling. Among these routes, the one called ''ATRAP'', not much studied in the literature yet, was finally retained. The physical-chemical properties of the so-synthesized materials, grafted with different lateral chains, were determined by different characterization techniques and their application in thin films for Organic Photovoltaic devices was performed. When used as additives, these materials display a potential of stabilizing the P3HT/PC60BM layer, and this does not influence the performance of the device. After a thermal treatment, this behavior was the opposite of the expected, though: a destabilization of the active layer was noted which mechanism was also studied by several experimental techniques. Finally, a depolymerization mechanism induced by light and/or heat was proposed. Within this process, the cleavage of the monomer-fullerene bond is responsible for creating defects, such as the depolymerization, cross-linkings or irreversible rearrangement of the thin layer. This cleavage can be either thermally activated or induced by the triplet state of the monomer, which also destabilizes this bond. Beyond that, this work was also interested i) to the stabilization of the organic-inorganic interface within photovoltaic devices, ii) to the stabilization of the lateral chain of conjugated polymers, as well as iii) the relation between the geometry of a carbon-based molecule and its reactivity to molecular oxygen. These studies, performed in parallel, drove to the proposition of new donor-acceptor hybrid materials based on hexabenzocoronene, which are capable of stacking over itself to form supramolecular structures similar to discotic liquid crystals. From the conclusions of this document, two products were proposed, which electronic properties reveal that it is possible to design new materials that may be stable and efficient at the same time for application in organic photovoltaics.

O objetivo desta dissertação é estudar os efeitos estruturais e eletrônicos em fulerenos menores e C60 causados pela dopagem substitucional com boro e nitrogênio para aplicações em eletrônica molecular. Estudamos as propriedades eletrônicas e estruturais de possíveis retificadores moleculares formados por pares de fulerenos menores dopados com boro e nitrogênio. A molécula C@C59N foi estudada e suas propriedades estruturais e eletrônicas comparadas com as do endofulereno N@C60. No estudo da dopagem dos fulerenos utilizamos o método semiempírico Parametric Method 3 (PM3). Foram calculadas as geometrias de equilíbrio e os calores de formação, que serviram para investigar a estabilidade relativa dessas moléculas. Para cada dopante identificamos os sítios de substituição que mais favorecem à estabilidade termodinâmica das moléculas. Dentre todos os fulerenos menores estudados os isômeros do C5o atingiram a maior estabilidade quando comparados com o C60. Com os pares de moléculas mais estáveis obtidas no trabalho anterior, montamos os retificadores em uma estrutura do tipo D-ponte-A, onde D e A representam doador e aceitador de elétrons. Para as moléculas isoladas, calculamos as estruturas eletrônicas através da Teoria do Funcional da Densidade (DFT) com o funcional BLYP e a base 6-31G*. No caso dos pares usamos o método DFT com o funcional BSLYP e a base 3-21G* para obter as geometrias de equilíbrio e as estruturas eletrônicas. Aplicando um campo elétrico sobre as moléculas, investigamos a facilidade de transferência de cargas entre fulerenos. Concluímos que fulerenos menores possuem um grande potencial para construção de um diodo molecular. As propriedades da molécula hipotética C@C59N foram comparadas com as bem Conhecidas C60, C59N e N@C60. A energia de ligação por átomo da molécula é comparável às energias de ligação dos outros fulerenos, em particular do seu isômero N@C60. Devido à tendência dos azafulerenos em formar dímeros, verificamos a estabilidade da molécula N@C60 quando comparada com o dímero N@C60 )2. . Tanto as geometrias quanto as estruturas eletrônicas foram calculados via DFT, BSLYP/6-31G*. Concluímos deste estudo que a molécula C@Ge¡/ é estável energeticamente, como também a interessante possibilidade do uso do dímero (C@C59N)2 como um bit quântico. / The present dissertation is devoted to the study of the effects on small fullerenes and 060 caused by the substitutional doping of boron and nitrogen for applications in molecular electronics. Electronic and structural properties of molecular rectifiers formed by small fullerenes doped with boron and nitrogen have been studied. The molecule C@C59 N has been investigated and its structural and electronic properties compared with those of the endofullerene N@C60 To study the doping of the fullerenes we used the semiempirical method Para­ metric Method 3 (PM3). Ground state conformations and heats of formation were obtained and used to investigate the relative molecular stability. We indentified the most favorable molecular substitution sites for the thermodynamic stability of each dopant. Among all small fullerenes investigated, the isomers of C50reached the largest stability when compared with 060 Molecular rectifiers with a structure of the type D-bridge-A, where D and A indicate electron donor and acceptor, respectively, were built with the most stable pairs found in the previous part of. The Density Functional Theory (DFT) with the functional BLYP and the base 6-31G* was used to calculate the electronic struc­ tures of the isolated molecules. Geometry optimizations and electronic structures of the pairs, were carried by DFT, B3LYP j3 21G*, method. The asymmetry of the charge transfer was assessed through the application of an externai electric field. We concluded that small fullerenes are promising candidates for the construction of molecular rectifiers. The properties of the hypothetical molecule C@C59 N were compared with those well known C60 , C59 N e N@C60 molecules. The binding energy of this molecule is comparable with that of the other fullerenes, in particular with that of its isomer N@C60 Due to the tendency of the azafullerene in forming dimers, the stability of the dimer (C@C59 N)2 was investigated. The molecular conformations and the electronic structures were obtained by the DFT, B3LYP/6-31G*, method. We con­ cluded that (C@C59 N) 2 molecule should be as stable as the azafullerene dimer. Our results point to the interesting possibility of using this system as a quantum bit.

Because the gel-spinning process has the potential to yield fibers of high strength and high modulus, this technique was employed to process continuous filaments of PVA/CNT, having CNTs at ¡Ü1 weight percent of polymer. A gel aging technique was employed with the goal of increasing the draw ratio for composite fibers and for promoting the development of crystalline PVA. Since residual solvent can lower the mechanical properties of drawn fibers, solvent phases of water and dimethyl sulfoxide (DMSO) within the drawn fibers were also characterized. As embedded SWNTs were uniaxially aligned along the drawn fiber axis, they were found to induce preferential alignment in the PVA side groups as well as for the residual solvent. This was attributed to charge transfer between SWNT and the respective functional groups. This orientation behavior has been characterized using Raman spectroscopy and infra-red dichroism. The behaviors of gel crystallization and solvent freezing within PVA/CNT dispersions were studied using thermal analysis and rheology. Carbon nanotubes were found to nucleate PVA crystallization in the gel state. PVA/CNT gel aging behavior was characterized by structural, thermal, and mechanical, and dynamic mechanical means. Gel aging was shown to increase the draw ratio of PVA/CNT fibers, and the development of the higher temperature melting peak was attributed to the draw induced ordering of PVA along CNTs. The scanning electron micrographs of fractured PVA/CNT fibers showed fibrils having an average diameter of about 22 nm. The storage modulus of aged gel was a function of solvent diffusion, which changed with aging time. CNTs were shown to have stabilized the gel network, as characterized by the dynamic mechanical properties, and to provide nucleation sites for the ordering of PVA chains, as characterized by WAXD.

In this thesis, We have calculated the optimized geometries, electronic structures and spin distributions of metal and non-metal elements Li, Na, N and P doped C60 fullerene dimers and trimers with different spin multiplicities using hybrid density functional theory (DFT) at the B3LYP/6-31G level of theory. Natural population analysis and Mulliken population analysis show that non-metal elements (N, P) inside the C60 fullerene dimers and trimers are well isolated and preserve their electronic structures while charge transfer processes occur between metal elements(Li, Na) and C60 structures. Energy calculations showed that both doped and undoped linear C60 structures are energetically lower than triangular C60 structures. Calculated spin density distributions make non-metal doped C60 structures advantageous over metal doped C60 cages as spin cluster qubits.

Fullerene research has advanced to elevated levels in a short period of time due to the unique chemical and physical properties of the caged molecule that have been utilized in numerous applications. Due to the spherical shape of the fullerene molecule which allows for a hollow cavity, encapsulation of atoms or small molecules can occur within the ball structure. This encapsulation creates an endohedral component that is limited from interacting with other molecules which creates potential of control over electronic information of the isolated molecule. Endohedral fullerenes have the potential as serving as the base unit in a quantum computer if control over global alignment is attained. Thus, by using the inherent self-assembling capabilities of some organic materials, ordered endohedral fullerenes can be achieved. This dissertation investigates the ability to use self-assembling strategies to obtain alignment which include ordering within a morphologically controlled copolymer matrix, forming a supramolecular polymer complex with cyclodextrin, and encapsulation within the helical wrap of polymer chains. The ultimate goal is to understand the dynamics that control association and orientation of varying fullerene-based molecules in each strategy in order to maximize control over the final alignment of endohedral elements.

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Two different interfaces were the focus of study: 1) the interface between disordered amorphous carbon and inorganic materials (metal nanostructures and silicon), and 2) the interface between partially ordered graphene (graphene oxide) and synthetic polymer matrix. Specifically, the uniqueness of this study can be summarized through the following novel findings, fabrication processes, and characterization techniques: • A simple and efficient process for faster, greener, less-expensive, and highly localized transformation of amorphous carbon nanostructures into graphitic nanostructures using low temperature heat and light treatments was developed for the fabrication of low-resistance interfaces between carbon nanomaterials and inorganic metal surfaces. • A new protocol for high resolution mapping the charge distribution and electronic properties of nanoscale chemically heterogeneous domains on non-homogeneous surfaces such as graphene oxide was established. • High strength laminated mechanical nanocomposites based on high interfacial stress transfer between polymer matrices and large area, flat, and non-wrinkled graphene oxide sheets were suggested and demonstrated. • Scanning Thermal Twist Microscopy – a thermal microscopy based technique was developed and demonstrated for characterizing the thermal properties of homogeneous and heterogeneous interfaces with nanoscale spatial resolution and high thermal sensitivity unachievable using traditional techniques.