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Huang, Yingsi. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2009. / Includes bibliographical references (leaves 105-106). / Abstracts in English and Chinese. / Abstract --- p.i / Abstract (in Chinese) --- p.iii / Acknowledgment --- p.v / Table of Contents --- p.vii / List of Figures --- p.x / List of Schemes --- p.xv / List of Tables --- p.xv / Abbreviations --- p.xvi / Chapter Chapter 1 --- Introduction --- p.1 / Chapter 1.1 --- Natural Photosynthesis --- p.1 / Chapter 1.1.1 --- Process of Natural Photosynthesis --- p.1 / Chapter 1.1.2 --- Chromophores of Natural Photosynthesis --- p.2 / Chapter 1.1.3 --- Mechanism of Natural Photosynthesis --- p.3 / Chapter 1.2 --- Development of Artificial Photosynthetic Models --- p.4 / Chapter 1.2.1 --- Models Based on Porphyrins and Fullerene Derivatives --- p.6 / Chapter 1.2.2 --- Models Based on Boron Dipyrromethenes (BDPs) --- p.12 / Chapter 1.2.3 --- Applications of Artificial Photosynthetic Models --- p.14 / Chapter 1.3 --- Boron Dipyrromethenes (BDPs) --- p.15 / Chapter 1.3.1 --- General --- p.15 / Chapter 1.3.2 --- Energy Transfer Systems Based on BDPs --- p.16 / Chapter 1.3.2.1 --- BDPs as Energy Donors --- p.16 / Chapter 1.3.2.2 --- BDPs as Energy Acceptors --- p.22 / Chapter 1.3.2.3 --- BDPs as both Energy Donors and Acceptors --- p.26 / Chapter 1.4 --- References --- p.30 / Chapter Chapter 2 --- "Synthesis, Characterization, and Photophysical Properties of the Triad BDP-SiPc-MSBDP as an Artificial Photosynthetic Model" --- p.35 / Chapter 2.1 --- Introduction --- p.35 / Chapter 2.2 --- Results and Discussion --- p.38 / Chapter 2.2.1 --- Preparation and Characterization --- p.38 / Chapter 2.2.2 --- Electronic Absorption and Photophysical Properties --- p.45 / Chapter 2.2.3. --- Electrochemical Properties --- p.50 / Chapter 2.3 --- Conclusion --- p.52 / Chapter 2.4 --- Experimental Section --- p.52 / Chapter 2.4.1 --- General --- p.52 / Chapter 2.4.2 --- Photophysical Studies --- p.53 / Chapter 2.4.3 --- Electrochemical Studies --- p.54 / Chapter 2.4.4 --- Synthesis --- p.54 / Chapter 2.5 --- References --- p.58 / Chapter Chapter 3 --- "Synthesis, Characterization, and Photophysical Properties of the Pentad SiPc(MSBDP-BDP)2" --- p.60 / Chapter 3.1 --- Introduction --- p.60 / Chapter 3.2 --- Results and Discussion --- p.61 / Chapter 3.2.1 --- Preparation and Characterization --- p.61 / Chapter 3.2.2 --- Ground-State Electronic Properties and Energy Transfer Processes of BDP-MSBDP 3.3 --- p.66 / Chapter 3.2.3 --- Photophysical Properties of the Pentad SiPc(MSBDP-BDP)2 (3.1) --- p.68 / Chapter 3.2.4 --- Electrochemical Properties of the Pentad SiPc(MSBDP-BDP)2 (3.1) --- p.73 / Chapter 3.3 --- Conclusion --- p.75 / Chapter 3.4 --- Experimental Section --- p.75 / Chapter 3.4.1 --- General --- p.75 / Chapter 3.4.2 --- Synthesis --- p.75 / Chapter 3.5 --- References --- p.80 / Chapter Chapter 4 --- Novel Artificial Photosynthetic Models Constructed by Supramolecular Methodology --- p.81 / Chapter 4.1 --- Introduction --- p.81 / Chapter 4.2 --- Results and Discussion --- p.83 / Chapter 4.2.1 --- Preparation and Characterization --- p.83 / Chapter 4.2.2 --- Ground-state Electronic Properties and Energy Transfer Process of Compound 4.6 --- p.86 / Chapter 4.2.3 --- Formation and Properties of Assembly 4.1 (ZnTPP.4.6) --- p.89 / Chapter 4.2.4 --- Formation and Properties of Assembly 4.2 [Ru(CO)TPP.4.6] --- p.95 / Chapter 4.2.5 --- Comparison of the Assemblies 4.1 and 4.2 --- p.100 / Chapter 4.3 --- Conclusion --- p.101 / Chapter 4.4 --- Experimental Section --- p.101 / Chapter 4.4.1 --- General --- p.101 / Chapter 4.4.2 --- Synthesis --- p.102 / Chapter 4.5 --- References --- p.105

Zheng, Xing. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2010. / Includes bibliographical references. / Abstracts in English and Chinese. / Abstract --- p.iii / 摘要 --- p.iv / Acknowledgements --- p.v / Table of Contents --- p.vi / Chapter Chapter 1 --- Introduction --- p.1 / Chapter Chapter 2 --- Macrocycles based on Phenanthrene - Syntheses and Applications --- p.31 / Chapter 1. --- Project Aim and Molecule Design --- p.31 / Chapter 1.1. --- Project Aim --- p.31 / Chapter 1.2. --- Design of Molecules --- p.31 / Chapter 2. --- Synthesis of Macrocycles with Different Linkages --- p.37 / Chapter 2.2. --- Synthesis of Macrocycle with Monoacetylene Units as Linkages --- p.38 / Chapter 2.3. --- Synthesis of Macrocycle with Carbon-Carbon Double Bond as linkages --- p.45 / Chapter 2.4. --- Synthesis of Macrocycle with Carbon-Carbon Singe Bond as Linkages --- p.48 / Chapter 2.5. --- Synthesis of Macrocycle with Mixed Diacetylene and Acetylene Units as Linkages --- p.49 / Chapter 2.6. --- Synthesis of Macrocycle with Diacetylene Units as Linkages without Side Chains --- p.52 / Chapter 3. --- Characterization and Application of Macrocycles based on Phenanthrene --- p.53 / Chapter 3.1. --- Self-assembly of Macrocycles 2.1 --- p.53 / Chapter 3.2. --- Induced Ring Currents in Phenanthrene-Fused Dehydroannulenes --- p.58 / Chapter 3.3. --- Application as Fluorescence Sensors for Explosives --- p.62 / Chapter 3.4. --- Application as Organic Semiconductors --- p.62 / Chapter 3.5. --- Application as Precursors in Attempted Synthesis of Carbon Nano Belt and Polymeric Nanotubes --- p.64 / Chapter 4. --- Experiment --- p.68 / Appendix --- p.93

Lee, Man Ho. / Thesis submitted in: October 2008. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2009. / Includes bibliographical references (leaves 78-83). / Abstracts in English and Chinese. / Table of Contents --- p.ii / Acknowledgements --- p.iv / Abbreviations --- p.v / Abstract --- p.vi / Chapter Chapter 1 --- Introduction / Chapter 1.1 --- Definition of Aromatic Bond Activation --- p.1 / Chapter 1.2 --- Application of Aromatic Carbon Fluorine Bond Activation --- p.1 / Chapter 1.3 --- Mechanistic Schemes Involved in Aromatic Bond Activation --- p.2 / Chapter 1.4 --- Difficulties in Aromatic Bond Activation --- p.7 / Chapter 1.5 --- Competitive Bond Activations --- p.20 / Chapter 1.6 --- Structural Features of Rhodium Porphyrins --- p.27 / Chapter 1.7 --- Objective of the Work --- p.28 / Chapter Chapter 2 --- Competitive C-F and C-H Activation of Fluorobenzenes by Rhodium(III) Porphyrins / Chapter 2.1 --- C-F Activation of Fluorobenzene by Rhodium(III) Porphyrins --- p.29 / Chapter 2.2 --- Preparation of Starting Materials --- p.29 / Chapter 2.3 --- Base Effect of CFA --- p.30 / Chapter 2.4 --- Solvent Effect of CFA --- p.32 / Chapter 2.5 --- Temperature Effect of CFA Reaction --- p.34 / Chapter 2.6 --- Activations of Fluorobenzene --- p.35 / Chapter 2.7 --- Electronic Effect of Carbon-Fluorine Bond Activations --- p.38 / Chapter 2.8 --- Preliminary Mechanistic Studies --- p.39 / Chapter 2.9 --- Proposed C-F Activation Mechanism --- p.44 / Chapter 2.10 --- Proposed C-H Activation Mechanism --- p.48 / Chapter 2.11 --- Summary --- p.51 / Chapter Chapter 3 --- Experimental Section --- p.56 / References --- p.78 / Table of Content of Appendix --- p.83 / Appendix I Crystal Data and Processing Parameters --- p.85 / Appendix II Spectra --- p.91

Bulk and thin film samples of Bi₂₋[subscript x]Pb[subscript x]Sr₂Ca₂Cu₃O[subscript y] compounds were prepared by suitable methods. The thin film and bulk samples were exposed to argon gas at temperatures of about 2000 °C and pressures of about 300 atm. in a ballistic compressor (BC) and then cooled at a rate of about 10⁵ °C/sec. The samples before and after this treatment were examined and compared using a transmission electron microscope (TEM), a scanning electron microscope (SEM), an energy dispersive spectrometer (EDS) , and an x-ray diffractometer (XRD). Resistance and magnetic susceptibility measurements were made to determine changes in superconducting temperature Tc. Resistance and AC susceptibility measurements of bulk and thin film samples demonstrated that the Tc increased 3- 6 K after the BC treatment, and step-shaped curves were often observed in the resistance versus temperature graphs. The x-ray diffraction study revealed that the relative intensities of lines of the two high Tc phases clearly increased, and the relative intensities of lines of the low Tc phase decreased after the BC treatment. Scanning electron micrographs of the exposed samples showed that surface melting had occurred, and the BC treatment affected the surface of samples to a depth of about 10 μm. Energy dispersive spectral analysis showed that oxygen loss occurred in the exposure process. Transmission electron diffraction patterns showed that the crystal structure of the Bi-based compounds have an incommensurate modulation along the b-axis with different periods of 25.4 Å, 38.7 Å and 72.6 Å. After the BC treatment, the lattice parameters of superconductors did not change, but the relative intensities of spots changed, the modulation of 72.6 Å disappeared, and the density of twist boundaries increased. These observations suggest that the treatment changed the density of structural defects and the atomic arrangement. These studies tentatively indicate that the increase in structural defects was caused by oxygen loss. A very small oxygen loss increases the fraction of copper in CU‴ oxidation state, and thus increases the density of hole carriers in the Cu-O planes. This may be the reason why the Tc of Bi-based cuprate superconductors increased after the BC treatment.

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