Lai Chi-hung. / Thesis (M.Phil.)--Chinese University of Hong Kong, 1978. / Bibliography: leaves 80-82.

Thesis (M.Phil.)--Chinese University of Hong Kong. / Bibliography: leaves 94-96.

Peng Yu. / Thesis (M.Phil.)--Chinese University of Hong Kong, 1999. / Includes bibliographical references. / Abstracts in English and Chinese. / Table of Contents --- p.i / Acknowledgements --- p.iv / Abstract --- p.v / Abbreviations --- p.ix / Chapter CHAPTER 1. --- METALLATION OF AMINOPYRIDINE AND AMINOQUINOLINE / Chapter 1.1 --- INTRODUCTION / Chapter 1.1.1 --- General Background --- p.1 / Chapter 1.1.2 --- Synthesis of Metal Amides --- p.2 / Chapter 1.1.3 --- General Review of Lithium Amido Complexes --- p.4 / Chapter 1.1.4 --- Structures of Some Potassium and Sodium Amido Complexes --- p.8 / Chapter 1.1.5 --- A Brief Review of TV-functionalized Amido Metal Complexes --- p.9 / Chapter 1.1.6 --- Objective of This Work --- p.13 / Chapter 1.2 --- RESULTS AND DISCUSSION / Chapter 1.2.1 --- Synthesis of N-functionalized Amido Ligands --- p.14 / Chapter 1.2.2 --- Lithiation of Aminopyridine --- p.15 / Chapter 1.2.3 --- Lithiation of Aminoquinoline --- p.17 / Chapter 1.2.4 --- Attempted Synthesis of Sodium Amido Complexes --- p.19 / Chapter 1.2.5 --- Attempted Synthesis of Potassium Amido Complexes --- p.19 / Chapter 1.2.6 --- Physical Characterizations of and Compounds 1-10 --- p.20 / Chapter 1.2.7 --- "Molecular Structures of Compounds 3，4, 7, 8, and10" --- p.24 / Chapter 1.3 --- EXPERIMENTALS FOR CHAPTER 1 --- p.37 / Chapter 1.4 --- REFERENCES FOR CHAPTER 1 --- p.44 / Chapter CHAPTER 2. --- SYNTHESIS AND STRUCTURES OF GROUP12 AMIDO COMPLEXES / Chapter 2.1 --- INTRODUCTION / Chapter 2.1.1 --- General Review of Zinc(II) Amido Complexes --- p.49 / Chapter 2.1.2 --- General Review of Cadmium(II) Amido Complexes --- p.53 / Chapter 2.1.3 --- General Review of Mercury(II) Amido Complexes --- p.56 / Chapter 2.2 --- RESULTS AND DISCUSSION / Chapter 2.2.1 --- Synthesis of Homoleptic Zinc(II) Amido Complexes --- p.58 / Chapter 2.2.2 --- Attempted Reaction of Compounds [Zn(L1)2] and [Zn(L3)2] (11) with ArSH and S --- p.59 / Chapter 2.2.3 --- Attempted Reaction of [Zn(L1)Cl] with ArSLi and ArMe OLi --- p.59 / Chapter 2.2.4 --- Synthesis of Cadmium(II) Amido Complexes --- p.61 / Chapter 2.2.5 --- "Attempted Reaction of [{Cd(L3)2}2(tmeda)] (16) with S， Se, and ArSH" --- p.63 / Chapter 2.2.6 --- "Attempted Reaction of [Cd(L3)2] (15) with 4,4'- bipyridine" --- p.64 / Chapter 2.2.7 --- Synthesis of Mercury(II) Amido Complexes --- p.65 / Chapter 2.2.8 --- "Reaction of [Hg(L3)2] (21) with S, Se, and ArSH " --- p.67 / Chapter 2.2.9 --- Physical Characterizations of Compounds 11-23 --- p.68 / Chapter 2.2.10 --- "Molecular Structures of Compounds 11, 13, 16, and 21" --- p.73 / Chapter 2.3 --- EXPERIMENTALS FOR CHAPTER 2 --- p.84 / Chapter 2.4 --- REFERENCES FOR CHAPTER 2 --- p.94 / Chapter CHAPTER 3. --- SYNTHESIS AND STRUCTURES OF COPPER AND SILVER(I) AMIDO COMPLEXES / Chapter 3.1 --- INTRODUCTION / Chapter 3.1.1 --- Overview of Transition Metal Amides --- p.99 / Chapter 3.1.2 --- General Review of Copper Amido Complexes --- p.101 / Chapter 3.1.3 --- General Review of Silver(I) Amido Complexes and their Derivatives --- p.105 / Chapter 3.2 --- RESULTS AND DISCUSSION / Chapter 3.2.1 --- Synthesis of Homoleptic Copper(I) Amido Complexes --- p.108 / Chapter 3.2.2 --- Reaction of [{Cu(L3)}2] (24) with ArSH and Dioxygen --- p.110 / Chapter 3.2.3 --- Synthesis of Homoleptic Copper(II) Amido Complexes --- p.111 / Chapter 3.2.4 --- Attempted Reaction of CuCl2 with [{Li(L4)}3] (8) --- p.112 / Chapter 3.2.5 --- Attempted Reaction of [Cu(L3)2] (24) with ArSH --- p.112 / Chapter 3.2.6 --- Synthesis of Silver(I) Amido Complexes --- p.113 / Chapter 3.2.7 --- Attempted Reaction of AgN03 with [{Li(L4)}3] (8) --- p.114 / Chapter 3.2.8 --- Physical Characterizations of Compounds 24-29 --- p.115 / Chapter 3.2.9 --- "Molecular Structures of Compounds 24, 25, 26, and28" --- p.119 / Chapter 3.3 --- EXPERIMENTALS FOR CHAPTER 3 --- p.131 / Chapter 3.4 --- REFERENCES FOR CHAPTER 3 --- p.138 / Chapter CHAPTER 4. --- SYNTHESIS AND STRUCTURES OF NICKEL(II) AMIDO COMPLEXES / Chapter 4.1 --- INTRODUCTION / Chapter 4.1.1 --- General Review of Nickel Derivatives --- p.139 / Chapter 4.2 --- RESULTS AND DISCUSSION / Chapter 4.2.1 --- Synthesis of Homoleptic Nickel(II) Amido Complexes --- p.144 / Chapter 4.2.2 --- Attempted Reaction of NiCl2 with [Li(L3)(tmeda)] (3) --- p.145 / Chapter 4.2.3 --- Physical Characterizations of Compounds 30-32 --- p.145 / Chapter 4.2.4 --- Molecular Structures of Compounds 31 and 32 --- p.147 / Chapter 4.3 --- EXPERIMENTALS FOR CHAPTER 4 --- p.153 / Chapter 4.4 --- REFERENCES FOR CHAPTER 4 --- p.155 / Chapter APPENDIX 1 --- General Procedures and Physical Measurements --- p.157 / Chapter APPENDIX 2 --- "Table A-1. Selected Crystallographic Data for Compounds 3, 4, 7, and 8" --- p.160 / "Table A-2. Selected Crystallographic Data for Compounds 10, 11, 13，and 16" --- p.161 / "Table A-3. Selected Crystallographic Data for Compounds 21, 24, 25, and 26" --- p.162 / "Table A-4. Selected Crystallographic Data for Compounds 28，31, and 32" --- p.163

Kwong Wai-chuen. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2002. / Includes bibliographical references (leaves 98-102). / Abstracts in English and Chinese. / Acknowledgement --- p.I / Abstract (in English) --- p.II / Abstract (in Chinese) --- p.III / Abbreviation --- p.V / List of Compounds --- p.VI / Contents --- p.VII / Chapter Chapter 1. --- Introduction / Chapter 1.1 --- Metallacarboranes of the C2B4 Systems --- p.1 / Chapter 1.1.1 --- Group 1 Metallacarboranes of the C2B4 Systems --- p.3 / Chapter 1.1.2 --- Group 4 Metallacarboranes of the C2B4 Systems --- p.6 / Chapter 1.2 --- Group 4 Metallacarboranes of the C2B9 Systems --- p.17 / Chapter 1.3 --- Group 4 Metallacarboranes of the C2B10 Systems --- p.35 / Chapter 1.4 --- Applications of Group 4 Metallacarboranes --- p.44 / Chapter 1.5 --- Research Objectives --- p.47 / Chapter Chapter 2. --- Synthesis and Structural Characterization of Group4 Metallacarboranes of the C2B9 Systems / Chapter 2.1 --- Synthesis and Structural Characterization of {{466}4:η2-[(C6H5CH2)2C2B9H9]2ZrCl(THF)} {Na(THF)3} --- p.48 / Chapter 2.2 --- Synthesis and Structural Characterization of [η4:η2- {(C6H5CH2)2C2B9H9} 2ZrCl(THF)] [Li(THF)4] --- p.54 / Chapter 2.3 --- Synthesis and Structural Characterization of ZrCl[N(SiMe3)2]3 --- p.57 / Chapter 2.4 --- "Synthesis and Structural Characterization of η2-(C6H5CH2)2C2B9H9]M(NEt2)2(NHEt2HCH2Cl2) (M = Ti, Zr)" --- p.62 / Chapter 2.5 --- "Synthesis and Structural Characterization of [μ-{ o-C6H4(CH2)2 }C2B9H9]2M(THF)2 (M = Zr, Hf)" --- p.68 / Chapter 2.6 --- Conclusion --- p.71 / Chapter Chapter 3. --- Synthesis and Structural Characterization of Group4 Metallacarboranes of the C2B10 Systems / Chapter 3.1 --- "Synthesis and Structural Characterization of {{471}-l,，2-(o-C6H4(CH2)2)- 1,2-C2B 10H10]2Zr} {Na(THF)3}2 and {[μ-l，2-(o-C6H4(CH2)2)-l,2- C2B10H10]2ZrCl2} {Na(THF)3}2(THF)" --- p.72 / Chapter 3.2 --- Conclusion --- p.78 / Chapter Chapter4. --- Summary --- p.79 / Chapter Chapter5. --- Experimental Section --- p.81 / References --- p.98 / Appendix / Chapter I. --- Crystal Data and Summary of Data Collection and Refinement --- p.103 / Chapter II. --- Atomic Coordinates and Thermal Parameters --- p.109 / Chapter III. --- Bond Distances and Angles --- p.117

by Man Fai Shek. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2002. / Includes bibliographical references (leaves 86-90). / Abstracts in English and Chinese. / Chapter I. --- ABSTRACT --- p.1 / Chapter II. --- ACKNOWLEDGEMENTS --- p.4 / Chapter III. --- CONTENT PAGE --- p.5 / Chapter IV. --- INTRODUCTION --- p.6 / Chapter A. --- CHEMISTRY OF TETRAPHENYLENES --- p.6 / Chapter B. --- CLATHRATE INCLUSION CHARACTER OF TETRAPHENYLENES --- p.8 / Chapter C. --- SYNTHESIS OF TETRAPHENYLENE AND SUBSTITUTED TETRAPHENYLENES --- p.10 / Chapter 1. --- ELECTROPHILIC AROMATIC SUBSTITUTION APPROACH --- p.10 / Chapter 2. --- SUBSTITUTED BIPHENYLENE PYROLYSIS APPROACH --- p.12 / Chapter 3. --- ARYL-HALJDE COUPLING APPROACH --- p.14 / Chapter 4. --- BIS ACETYLENE APPROACH --- p.16 / Chapter D. --- "SYNTHESIS OF TRIBENZO[α, c, e]CYCLOOCTENE" --- p.18 / Chapter E. --- "SYNTHESIS OF SUBSTITUTED TRJBENZO[α,c,e]CYCLOOCTENE" --- p.21 / Chapter F. --- THE AIM OF THE PRESENT WORK --- p.25 / Chapter V. --- RESULTS AND DISCUSSION --- p.27 / Chapter 1. --- "SYNTHETIC STUDIES OF 1,4,5,16-TETRAHYDROXYTETRAPHENYLENE FROM 1,4- DIHYDROANTHRAQUINONE" --- p.27 / Chapter 2. --- SYNTHETIC STUDIES OF 1，4，5，16-TETRAHYDROXYTETRAPHENYLENE FROM1- AMINOANTHRAQUINONE --- p.41 / Chapter 3. --- "SYNTHETIC STUDIES OF 1,4, 5，16-TETRAHYDROXYTETRAPHENYLENE FROM 1，8- DIHYDROXYANTHRAQUINONE" --- p.46 / Chapter VI. --- CONCLUSION: --- p.53 / Chapter VII. --- EXPERIMENTAL --- p.57 / Chapter VIII. --- REFERENCES --- p.86 / Chapter IX. --- APPENDIX --- p.91

by Chi-Keung Lam. / Thesis (M.Phil.)--Chinese University of Hong Kong, 1998. / Includes bibliographical references (leaves 100-103). / Abstract also in Chinese. / Acknowledgments --- p.i / Abstract --- p.ii / 摘要 --- p.iii / Table of contents --- p.iv / Index of compounds --- p.v / List of tables --- p.vi / List of figures --- p.vii / Chapter Chapter 1. --- Introduction / Chapter 1.1 --- Some aspects of urea/thiourea inclusion chemistry --- p.1 / Chapter 1.2 --- General chemistry of monocyclic oxocarbons --- p.5 / Chapter 1.2.1 --- Synthesis of monocyclic oxocarbons --- p.5 / Chapter 1.2.2 --- Aromaticity of monocyclic oxocarbon anions --- p.20 / Chapter 1.2.3 --- Reactions of monocyclic oxocarbons --- p.25 / Chapter 1.3 --- Aim of the present research --- p.31 / Chapter Chapter 2. --- Description of crystal structures / Chapter 2.1 --- Urea-anion inclusion compounds --- p.32 / Chapter 2.1.1 --- Bis(tetra-n-propylammonium) squarate-urea-water (1/ 6/2) --- p.32 / Chapter 2.1.2 --- Tetra-n-butylammonium hydrogen squarate-urea-water (1/1/1) --- p.38 / Chapter 2.1.3 --- Bis(tetraethylammonium) squarate-tetraethylammonium hydrogen carbonate- urea-water (1/2/4/6) --- p.42 / Chapter 2.1.4 --- Bis(tetra-n-propylammonium) croconate-urea-water (1/5/2) --- p.47 / Chapter 2.2 --- Thiourea-anion inclusion compounds --- p.53 / Chapter 2.2.1 --- Bis(tetraethylammonium) squarate-thiourea-water (1/4/ 2) --- p.53 / Chapter 2.2.2 --- Bis(tetraethylammonium) squarate-thiourea (1/6) --- p.59 / Chapter 2.2.3 --- Bis(tetra-n-propylammonium) squarate-thiourea-water (1/ 4/2) --- p.66 / Chapter Chapter 3. --- Summary and discussion / Chapter 3.1 --- Urea/thiourea monocyclic oxocarbon anions inclusion compounds --- p.71 / Chapter 3.2 --- Structural features and topological correlations of the host lattices --- p.72 / Chapter 3.3 --- Hydrogen bonding and linkage modes of urea and thiourea molecules --- p.87 / Chapter Chapter 4. --- Experimental / Chapter 4.1 --- Preparation of crystals --- p.91 / Chapter 4.2 --- X-ray Crystallography --- p.93 / References --- p.100 / Appendix Atomic coordinates and thermal parameters of the new inclusion compounds --- p.104

本论文主要研究了红磷作为可见光光催化剂在光解水产生氢气方面的应用。所涉及到的催化剂有：纯红磷，万寿菊状的P/YPO₄中空微米球，以及CoP₂修饰的红磷。论文也会讨论WO₃/TiO₂微米六方片及微米棒的制备，并介绍这些新材料在光解水产生氧气方面的应用。 / 第一章：发现了红磷作为可见光光催化材料在光解水制氢气领域的应用。从羟基自由基的检测和光电响应的测量表明，红磷具有在光照下产生电子和空穴的性质。同时，光生电子还原水的能力亦通过理论计算所验证。此外，半导体性质测试表明红磷具有p型半导体的性质。 / 第二章：通过红磷与YCl₃水溶液的反应，合成了万寿菊状的P/YPO₄中空微米球。所得到的微米球由结晶YPO₄纳米片和无定形红磷组成。光解水产生氢气表明，含有53 wt % YPO₄的P/YPO₄的光催化活性是红磷的6倍。同时，文中进一步讨论了中空微米球的形成机理及其光催化活性提高的原因。 / 第三章：研究并证明了CoP₂可以作为红磷光解水产生氢气的共催化剂。CoP₂的修饰可以极大的提高红磷的光解水产氢效率。其中，含2 wt % CoP₂的CoP₂/P的光解水产生氢气的速率较红磷提高了75倍。而且，CoP₂作为共催化剂的效率优于传统贵金属共催化剂Pt。关于CoP₂的共催化机理，初步认为与Co离子的配位作用有关。 / 第四章：通过简单的沉淀、煅烧反应，制备了由WO₃和 TiO₂纳米颗粒组装而成的WO₃/TiO₂微米棒和微米片。可见光氧化水产生氧气测试表明， WO₃/TiO₂复合物的光催化活性为WO₃的2.5倍以上。提出利用“颗粒堆积模型来解释WO₃/TiO₂ 微米棒和微米片的形成机理。 / 第五章：发现了WO₃对甲基蓝染料有趣的吸附性质。首先，利用钨酸铵，四丙基氢氧化铵和氯化钾合成了WO₃纳米棒。所制备的WO₃表现出了对甲基蓝很强的快速吸附能力。而且，WO₃在5s内所吸附的甲基蓝的量与活性炭在30分钟内的吸附相当。此外，通过离子间的作用力和“印迹-吸附过程对WO₃吸附甲基蓝的特性进行了解释。 / This thesis focuses primarily on the development of red phosphorus based visible-light-driven photocatalysts for hydrogen production from water. These materials include pure red phosphorus, hierarchical P/YPO₄ hollow microspheres, and CoP₂ loaded red phosphors. The fabrication of WO₃/TiO₂ microrods and plates with enhanced photocatalytic water oxidation property is also discussed. / Chapter I:Red phosphorus was discovered as a new visible-light driven photocatalyst for H₂ formation from the reduction of water by photogenerated electrons. The detection of hydroxyl radicals and results from photoconductivity measurements confirmed the photogeneration of electrons from the red phosphorus. Theoretical calculations indicated that the reduction of water by photogenerated electrons would be energetically possible. Moreover, a P-type semiconductor behavior of red phosphorus was observed. / Chapter II:Hierarchical P/YPO₄ hollow microspheres with enhanced photocatalytic activity than the individual components for hydrogen formation were prepared. The composite was synthesized by the reaction from amorphous red P and YCl₃ aqueous solution via a hydrothermal method. The final product consisted of crystalline YPO₄ nanosheets and amorphous red phosphorus. The composite with 53 wt % YPO₄ was up to 6 times more active than red phosphorus under visible light irradiation. The formation mechanism of hierarchical microspheres and the enhanced photocatalytic activity were discussed. / Chapter III:CoP₂ loaded as a cocatalyst significantly enhanced the rate of H2₂ formation from water over red phosphorus under visible light irradiation. The rate of H₂ formation over red P was increased by up to 75 times when loaded with 2 wt % CoP₂. The performance of CoP₂ as a cocatalyst was even higher than that of Pt. The coordination effect of Co ions was proposed to explain the enhanced photocatalytic activity by CoP₂ loaded. / Appendix I:WO₃/TiO₂ microrods and microplates assembled from WO₃ and TiO₂ nanoparticles were prepared by simple precipitation and calcination processes. Their photocatalytic properties for O₂ formation from water were investigated. The composites were c.a. 2.5 times more active than WO₃ in photocatalytic O₂ formation under visible light irradiation. The formation mechanism of WO₃/TiO₂ microstructures was explained from “particle packing mode“. / Appendix II:An interestingly adsorption property of hexagonal tungsten trioxide to MB was discovered. The WO₃ were prepared from ammonium metatungstate, tetrapropyl ammonium hydroxide and potassium chloride. The product exhibited a high adsorption capacity toward methylene blue (MB), and the time required for reaching adsorption equilibrium was less than 5 seconds. The amount of MB adsorbed by WO₃ in 5 s was equivalent to that adsorbed by activated carbon for 30 min. Ionic interaction and “imprinting-adsorption“ were proposed to explain the adsorption property of as-prepared WO₃ sample. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Wang, Feng. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2012. / Includes bibliographical references. / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstract also in Chinese. / Abstract (Chinese) --- p.i / Abstract --- p.iii / Acknowledgement --- p.vi / List of Figures --- p.viii / List of Tables --- p.xviii / Chapter Chapter 1 --- Introduction --- p.1 / Chapter 1.1 --- Basic Principles of Photocatalytic Water Splitting --- p.1 / Chapter 1.2 --- Strategies to Develop Visible-light-driven Photocatalysts --- p.3 / Chapter 1.2.1 --- Native visible-light-driven photocatalysts --- p.3 / Chapter 1.2.2 --- Doping --- p.6 / Chapter 1.2.2.1 --- Metal or non-metal ions doping --- p.6 / Chapter 1.2.2.2 --- Co-doping --- p.10 / Chapter 1.2.2.3 --- Homogeneous doping --- p.12 / Chapter 1.2.3 --- Solid solution photocatalysts --- p.15 / Chapter 1.2.4 --- Dye sensitized photocatalysts --- p.17 / Chapter 1.3 --- Strategies to Enhance Photocatalytic Efficiency --- p.19 / Chapter 1.3.1 --- Semicondutor combination --- p.19 / Chapter 1.3.1.1 --- Inorganic sensitization --- p.20 / Chapter 1.3.1.2 --- Bidirectional charge-carrier transfer --- p.21 / Chapter 1.3.1.3 --- Indirect Z-scheme --- p.22 / Chapter 1.1.1.4 --- Direct Z-scheme --- p.23 / Chapter 1.3.2 --- Cocatalyst loading --- p.24 / Chapter 1.3.2.1 --- Noble metal cocatalysts --- p.24 / Chapter 1.3.2.2 --- Metal oxide cocatalysts --- p.25 / Chapter 1.3.2.3 --- Metal sulfide cocatalysts --- p.26 / Chapter 1.3.2.4 --- Mixed cocatalysts --- p.27 / Chapter 1.3.3 --- Hydrogen Generation Systems Containing Sacrificial Reagents --- p.32 / Chapter 1.4 --- Summary --- p.34 / Chapter 1.5 --- Aim of This Thesis and Its Significance --- p.35 / Chapter 1.6 --- References --- p.36 / Chapter Chapter Two --- Red Phosphorus: An Elemental Photocatalyst for Hydrogen Formation from Water under Visible Light Irradiation --- p.52 / Chapter 2.1 --- Introduction --- p.52 / Chapter 2.2 --- Experimental --- p.54 / Chapter 2.2.1 --- Synthesis --- p.54 / Chapter 2.2.1.1 --- Preparation of crystalline red phosphorus --- p.54 / Chapter 2.2.1.1 --- Preparation of red phosphorus films --- p.54 / Chapter 2.2.2 --- Characterization --- p.55 / Chapter 2.2.3 --- Gas evolution tests --- p.56 / Chapter 2.2.4 --- Detection of photogenerated OH radicals --- p.56 / Chapter 2.2.5 --- Computational details --- p.57 / Chapter 2.2.6 --- Photoconductivity measurements and electrical tests --- p.57 / Chapter 2.3 --- Results and Discussion --- p.59 / Chapter 2.4 --- Conclusions --- p.74 / Chapter 2.5 --- References --- p.75 / Chapter Chapter Three --- Hierarchical P/YPO4 Microsphere for Photocatalytic Hydrogen Production from Water under Visible Light Irradiation --- p.79 / Chapter 3.1 --- Introduction --- p.79 / Chapter 3.2 --- Experimental --- p.81 / Chapter 3.2.1 --- Synthesis --- p.81 / Chapter 3.2.2 --- Characterization --- p.81 / Chapter 3.2.3 --- Gas evolution tests --- p.82 / Chapter 3.3 --- Results and Discussion --- p.83 / Chapter 3.4 --- Conclusions --- p.95 / Chapter 3.5 --- References --- p.95 / Chapter Chapter Four --- Enhancement of Photocatalytic H₂ Formation from Water over Red P by Loading CoP₂ as Cocatalyst --- p.99 / Chapter 4.1 --- Introduction --- p.99 / Chapter 4.2 --- Experimental --- p.100 / Chapter 4.2.1 --- Synthesis --- p.100 / Chapter 4.2.2 --- Characterization --- p.101 / Chapter 4.2.3 --- Hydrogen formation tests --- p.101 / Chapter 4.3 --- Results and Discussion --- p.103 / Chapter 4.4 --- Conclusions --- p.109 / Chapter 4.5 --- References --- p.109 / Chapter Chapter Five --- Conclusions and Future Work --- p.112 / Chapter 5.1 --- Conclusions --- p.112 / Chapter 5.2 --- Recommendations for future work --- p.112 / Chapter Appendix I --- WO₃/TiO₂ Microstructures for Photocatalytic Water Oxidation under Visible Light Irradiation --- p.114 / Chapter AI.1 --- Introduction --- p.114 / Chapter AI.2 --- Experimental --- p.116 / Chapter AI.2.1 --- Sample preparation --- p.116 / Chapter AI.2.1.1 --- Precursor synthesis --- p.116 / Chapter AI.2.1.2 --- Synthesis of assembled WO₃/TiO₂ microstructures --- p.118 / Chapter AI.2.2 --- Characterization --- p.119 / Chapter AI.2.3 --- Oxygen formation tests --- p.120 / Chapter AI.3 --- Results and Discussion --- p.121 / Chapter AI.4 --- Conclusions --- p.137 / Chapter AI.5 --- References --- p.137 / Chapter Appendix II --- Hexagonal Tungsten Trioxide Nanorods as a Rapid Adsorbent for Methylene Blue --- p.142 / Chapter AII.1 --- Introduction --- p.142 / Chapter AII.2 --- Experimental --- p.143 / Chapter AII.2.1 --- Sample preparation --- p.143 / Chapter AII.2.2 --- Characterization --- p.144 / Chapter AII.3 --- Results and Discussion --- p.145 / Chapter AII.4 --- Conclusions --- p.159 / Chapter AII.5 --- References --- p.159 / List of Publications --- p.163

酞菁是一種廣泛應用的多用途功能材料。本研究工作的目的是探索酞菁作為用於靶向光動力療法 (PDT) 的可激活的和高效光敏劑的潛力。就這研究課題，本論文描述了ー系列精心設計的酞菁光敏劑的合成、其光譜表徵、光物理屬性和體外光動力活性。 / 第一章概述了光動力療法，包括其歷史發展、光物理和生物機制及臨床應用現狀。本章介紹各種不同類型的光敏劑，其中重點介紹了酞菁，因它被視為最有前途的第二代光敏劑之一。為了提高療效，過往有不少努力都投放在去把光敏劑功能化，以實現它在化學療法和光動力雙效治療及靶向治療的作用。本章的結尾部分，我們更會引用相關的例子去討論和解釋這種先進治療方式的概念以及近期的發展。 / 含鉑藥物已作為臨床化療藥物廣泛應用於多種癌症的治療。我們設計了一種新型的酞菁鉑配合物共軛體系，以取得光動力和化學療法的雙重效果。第二章主要描述了由鋅(II)酞菁和具有抗癌性的奧沙利鉑衍生物構成的共軛體系的合成方法和光譜特性，同時對該共軛體系基本的光物理性能，聚合行為和體外光動力性能進行了考察，並與一些化合物模型進行了對比。該共軛體系展示出一種協同效應。在HT29 人結腸腺癌細胞內，奧沙利鉑的存在導致該共軛體系在黑暗裡產生暗毒性；在光照下，基於鋅(II)酞菁的存在，它產生了增强的細胞毒素效應。這種高效光動力行為也可以歸結為其較高的細胞攝取和活性氧 (ROS) 產生的功效。該共軛體系更傾向定位於細胞溶酶體並誘使主要通過細胞凋亡的細胞死亡。 / 多胺是普遍存在於細胞的陽離子，並在細胞的繁殖和分化中起着多重作用。許多腫瘤細胞表現出具有較高的多胺含量並且激活多胺載體以導入外源多胺來維持快速的細胞分裂活動。因此，與多胺類化合物的結合是提高光敏材料針對腫瘤細胞的方法之一。第三章描述了一系列多胺取代的鋅(II)酞菁的合成、光譜表徵和光物理特性，並考察了它們對於B16 黑色素瘤和中國倉鼠卵巢 CHO 細胞的光動力行為。同時對其細胞攝取率、亞細胞定位和細胞死亡機制進行了報導。 / 除了與這些腫瘤特異載體共軛連接，可被腫瘤相關刺激激活的光敏劑也是能提高腫瘤選擇性的一個好方法。谷胱甘肽 (GSH) 在細胞質中是最豐富的硫醇，也是在生物化學過程中主要的還原劑。細胞內的谷胱甘肽 (ca. 10 mM) 與細胞外部 (ca. 2 μM) 相比具有較高的濃度。 因此，我們可以利用以這個特性來啟動光敏劑。第四章報告了一種具有還原效應的矽(IV)酞菁。該化合物軸向由兩個二茂鐵基查爾酮衍生物通過二硫鍵取代，並易於在還原條件下快速斷裂。我們通過不同的光譜測試，對該化合物基本的光物理性能及其在還原試劑作用下的斷裂動力學進行了研究。我們也同時考察了存在和不存在外部還原試劑條件下，其對於MCF-7 人乳腺癌細胞的體外光動力行為，包括細胞毒素效應、細胞攝取和亞細胞定位。 / 為了進一步提高腫瘤的選擇性，發展一種可同時被兩種腫瘤相關刺激激活的光敏劑也是體現靶向治療的方法之一。 癌細胞除了比正常細胞含有較高的谷胱甘肽濃度外，它的另一種特性是其外區域的pH 值 (ca. 6.8) 比周圍正常組織(ca. 7.3) 相對較低。這種獨特的特徵也是一種機制來啟動光敏劑。第五章主要探討一種具有pH 和還原雙回應的矽(IV)酞菁。該化合物軸向分別由二茂鐵衍生物通過二硫鍵和腙鍵取代。由於連接鍵在生理的pH 值和低濃度還原試劑或其中一項的條件下不會斷裂，所以在二茂鐵的淬滅的影響下，光敏劑維持在光動力惰性的狀態。但是，在酸性和高濃度還原試劑的情況下，光敏劑會被激活。我們會在這一章探討這些外來刺激對光敏劑的光物理特性和體外光動力行為的影響。 / 第六章會就本項研究作出總結，而第七章則報導實驗程序。第八章列舉了本論文所引用的參考文獻。 / 論文的最後會附上所有新化合物的氫及碳核磁共振譜圖。 / Phthalocyanines are versatile functional materials for a wide range of applications. This research work aims to explore their potential as activatable and efficient photosensitizers for targeted photodynamic therapy (PDT). This thesis describes the synthesis, spectroscopic characterization, photophysical properties, and in vitro photodynamic activities of several series of carefully designed phthalocyanine-based photosensitizers. / Chapter 1 presents an overview of PDT, including its historical development, photophysical and biological mechanisms, and current clinical applications. Various classes of photosensitizers are introduced with emphasis put on phthalocyanines, which have emerged as a promising class of second-generation photosensitizers for PDT. In order to enhance the therapeutic efficacy, considerable effort has been expended to functionalize the photosensitizers with a view to achieving dual and targeted therapy. The concept and recent development of this advanced modality is discussed and illustrated with relevant examples at the end of this chapter. / Platinum-based drugs have been widely used as clinical chemotherapeutic drugs for the treatment of a variety of cancers. In order to bring about a dual photodynamic and chemotherapeutic effect, we have designed a novel phthalocyanine-platinum complex conjugate. Chapter 2 presents the synthesis and spectroscopic characterization of this conjugate, which comprises of a zinc(II) phthalocyanine and an oxaliplatin derivative that is known to have antitumor activity. The basic photophysical properties, aggregation behavior, and in vitro photodynamic activities of this conjugate have also been investigated and compared with those of some model compounds. This conjugate demonstrates a synergistic effect in which it shows a cytotoxic effect in the dark due to the oxaliplatin moiety and an enhanced cytotoxicity upon illumination due to the phthalocyanine unit toward the HT29 human colon adenocarcinoma cells. The high photodynamic activity can also be attributed to its higher cellular uptake and reactive oxygen pecies (ROS) generation efficiency. This conjugate shows preferential localization in the lysosomes and induces cell death mainly through apoptosis. / Polyamines are ubiquitous cellular cations that play multifunctional roles in cell proliferation and differentiation. Many tumors cells have been shown to contain elevated polyamine levels and active polyamine transporters for importing exogenous polyamines in order to sustain rapid cell division. As a result, conjugation of polyamine analogues is one of the potential strategies to improve the tumor-targeting property of photosensitizers. Chapter 3 describes the synthesis, spectroscopic characterization, and photophysical properties of a series of polyamine-substituted zinc(II) phthalocyanines. Their photodynamic activities toward B16 melanoma and Chinese hamster ovary (CHO) cells have been investigated. Their cellular uptake, subcellular localization, and cell death mechanism are also reported herein. / Apart from conjugation to these tumor-specific vectors, the use of photosensitizers that can be activated by tumor-associated stimuli is also a promising approach to enhance the tumor selectivity. Glutathione (GSH) is the most abundant thiol in cytoplasm and the major reducing agent in many biochemical processes. The much higher intracellular GSH concentration (ca. 10 mM) compared with the extracellular levels (ca. 2 μM) provides a mechanism for activating photosensitizers. Chapter 4 reports the molecular design and development of a novel redox-responsive silicon(IV) phthalocyanine axially substituted with two ferrocenyl-chalcone derivatives via disulfide bonds, which are prone to rapid cleavage under a reducing environment. The basic photophysical properties of this compound and its cleavage kinetics upon exposure to a reductive stimulant have been studied by various spectroscopic methods. Its in vitro photodynamic activities including cytotoxicity, cellular uptake, and subcellular localization towa d MCF-7 human breast cancer cells, both in the absence and presence of an external reducing agent, have also been examined. / To further enhance the tumor specificity, development of activatable photosensitizers that can be activated concurrently by two different tumor-associated stimuli is also a promising strategy toward targeted PDT. Aside from the difference in GSH content between tumor and normal tissues, another unique feature of tumors is that their extracellular pH (ca. 6.8) is relatively lower as compared with that around the normal tissues (ca. 7.3). This characteristic offers another mechanism to trigger the response of photosensitizers. Chapter 5 focuses on the exploration of a dual pH- and redox-responsive silicon(IV) phthalocyanine in which the ferrocenyl quenchers are axially coordinated to the macrocycle through an acid-labile hydrazone bond and a reducible disulfide bond. At physiological pH and low level of reducing agent, or under one of these conditions, the linker(s) remain(s) intact and hence the photosensitizer remains photodynamically “inactive“ due to the quenching effect induced by the ferrocenyl unit(s). However, it becomes activated in an environment with low pH and high level of reducing agent, which is analogous to the conditions in tumor tissues. The effects of these external stimuli on the photophysical properties and in vitro photodynamic activities of this novel photosensitizer are examined in this chapter. / Chapter 6 concludes the present study while Chapter 7 reports the experimental procedures. All references adapted in this manuscript are presented in Chapter 8. / ¹H and ¹⁶C{¹H} NMR spectra of all the new compounds are given in the Appendix. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Lau, Ting Fong Janet. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2012. / Includes bibliographical references (leaves 191-202). / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstract also in Chinese. / Table of Contents --- p.i / Acknowledgment --- p.vi / Abstract --- p.ix / Abstract (in Chinese) --- p.xii / Abbreviations --- p.xiv / List of Figures --- p.xviii / List of Tables --- p.xxvi / List of Schemes --- p.xxviii / Publication Related to This Thesis --- p.xxx / Chapter Chapter 1 --- Introduction / Chapter 1.1 --- Introduction --- p.1 / Chapter 1.1.1 --- History of Photodynamic Therapy --- p.1 / Chapter 1.1.2 --- Basic Principles of Photodynamic Therapy --- p.4 / Chapter 1.1.2.1 --- Photophysical Mechanisms --- p.4 / Chapter 1.1.2.2 --- Biological Mechanisms --- p.7 / Chapter 1.2 --- Photosensitizers of Photodynamic Therapy --- p.8 / Chapter 1.2.1 --- Characteristics of Ideal Photosensitizers --- p.10 / Chapter 1.2.2 --- First-Generation Photosensitizers --- p.11 / Chapter 1.2.3 --- Second-Generation Photosensitizers --- p.13 / Chapter 1.2.4 --- Phthalocyanine-Based Photosensitizers --- p.17 / Chapter 1.3 --- Toward Targeted Photodynamic Therapy --- p.23 / Chapter 1.3.1 --- Site-Specific Delivery of Photosensitizers --- p.23 / Chapter 1.3.1.1 --- Conjugation to Monoclonal Antibodies --- p.23 / Chapter 1.3.1.2 --- Conjugation to Tumor Vessel-Targeted Peptides --- p.24 / Chapter 1.3.1.3 --- Conjugation to Folic Acid --- p.26 / Chapter 1.3.2 --- Activatable Photosensitizers --- p.27 / Chapter 1.3.2.1 --- Environmental Activatable Photosensitizers --- p.27 / Chapter 1.3.2.2 --- Photodynamic Molecular Beacons --- p.30 / Chapter 1.4 --- Dual Chemo- and Photodynamic Therapy --- p.34 / Chapter 1.4.1 --- Covalent Conjugation --- p.34 / Chapter 1.4.2 --- Co-encapsulation in Polymeric Micelles --- p.36 / Chapter 1.4.3 --- Sequential Administration --- p.38 / Chapter 1.5 --- Objectives of This Study --- p.41 / Chapter Chapter 2 --- A Zinc(II) Phthalocyanine Conjugated with an Oxaliplatin Derivative for Dual Chemo- and Photodynamic Therapy / Chapter 2.1 --- Introduction --- p.42 / Chapter 2.2 --- Results and Discussion --- p.43 / Chapter 2.2.1 --- Molecular Design, Synthesis, and Characterization --- p.43 / Chapter 2.2.2 --- Electronic Absorption and Photophysical Properties --- p.46 / Chapter 2.2.3 --- In Vitro Photodynamic Activities --- p.49 / Chapter 2.3 --- Summary --- p.60 / Chapter Chapter 3 --- Zinc(II) Phthalocyanine-Polyamine Conjugates as Efficient Photosensitizers for Photodynamic Therapy / Chapter 3.1 --- Introduction --- p.62 / Chapter 3.2 --- Results and Discussion --- p.64 / Chapter 3.2.1 --- Preparation and Characterization --- p.64 / Chapter 3.2.2 --- Electronic Absorption and Photophysical Properties --- p.68 / Chapter 3.2.3 --- In Vitro Photodynamic Activities --- p.74 / Chapter 3.3 --- Summary --- p.84 / Chapter Chapter 4 --- A Redox-Responsive Silicon(IV) Phthalocyanine for Targeted Photodynamic Therapy / Chapter 4.1 --- Introduction --- p.85 / Chapter 4.2 --- Results and Discussion --- p.86 / Chapter 4.2.1 --- Preparation and Characterization --- p.86 / Chapter 4.2.2 --- Electronic Absorption and Photophysical Properties --- p.89 / Chapter 4.2.3 --- In Vitro Photodynamic Activities --- p.99 / Chapter 4.3 --- Summary --- p.104 / Chapter Chapter 5 --- A Dual pH- and Redox-Responsive Phthalocyanine-Based Photosensitizer for Targeted Photodynamic Therapy / Chapter 5.1 --- Introduction --- p.106 / Chapter 5.2 --- Results and Discussion --- p.107 / Chapter 5.2.1 --- Molecular Design, Synthesis, and Characterization --- p.107 / Chapter 5.2.2 --- Electronic Absorption and Photophysical Properties --- p.115 / Chapter 5.2.3 --- pH- and Redox-Responsive Properties --- p.118 / Chapter 5.2.4 --- In Vitro Photodynamic Activities --- p.130 / Chapter 5.3 --- Summary --- p.136 / Chapter Chapter 6 --- Conclusion and Future Outlook --- p.137 / Chapter Chapter 7 --- Experimental Section / Chapter 7.1 --- General --- p.138 / Chapter 7.1.1 --- Materials and Methods --- p.138 / Chapter 7.1.2 --- Photophysical Measurements --- p.139 / Chapter 7.1.3 --- Cell Lines and Culture Conditions --- p.140 / Chapter 7.1.4 --- Photocytotoxicity Assay --- p.141 / Chapter 7.1.5 --- ROS Measurements --- p.141 / Chapter 7.1.6 --- Intracellular Fluorescence Studies --- p.142 / Chapter 7.1.7 --- Cellular Uptake Determined by an Extraction Method --- p.142 / Chapter 7.1.8 --- Subcellular Localization Studies --- p.143 / Chapter 7.1.9 --- Flow Cytometric Studies --- p.144 / Chapter 7.2 --- Experiments Described in Chapter 2 --- p.145 / Chapter 7.2.1 --- Synthesis --- p.145 / Chapter 7.2.2 --- Photocytotoxicity Assay --- p.155 / Chapter 7.2.3 --- Intracellular Fluorescence Studies --- p.155 / Chapter 7.2.4 --- Cellular Uptake Determined by an Extraction Method --- p.155 / Chapter 7.2.5 --- Subcellular Localization Studies --- p.156 / Chapter 7.3 --- Experiments Described in Chapter 3 --- p.156 / Chapter 7.3.1 --- Synthesis --- p.156 / Chapter 7.3.2 --- Photocytotoxicity Assay --- p.171 / Chapter 7.3.3 --- Effect on Spermidine on the Cellular Uptake --- p.171 / Chapter 7.3.4 --- Intracellular Fluorescence Studies --- p.172 / Chapter 7.3.5 --- Subcellular Localization Studies --- p.172 / Chapter 7.4 --- Experiments Described in Chapter 4 --- p.173 / Chapter 7.4.1 --- Synthesis --- p.173 / Chapter 7.4.2 --- Redox-Responsive Fluorescence Emission Studies --- p.180 / Chapter 7.4.3 --- Redox-Responsive Singlet Oxygen Generation Studies --- p.180 / Chapter 7.4.4 --- Photocytotoxicity Assay --- p.180 / Chapter 7.4.5 --- Intracellular Fluorescence Studies --- p.181 / Chapter 7.4.6 --- Subcellular Localization Studies --- p.181 / Chapter 7.5 --- Experiments Described in Chapter 5 --- p.182 / Chapter 7.5.1 --- Synthesis --- p.182 / Chapter 7.5.2 --- pH- and Redox-Responsive Fluorescence Emission Studies --- p.189 / Chapter 7.5.3 --- pH- and Redox-Responsive Singlet Oxygen Generation Studies --- p.189 / Chapter 7.5.4 --- Intracellular Fluorescence Studies --- p.190 / Chapter Chapter 8 --- References --- p.191 / Chapter Appendix --- ¹H and ¹³C{¹H} NMR Spectra --- p.203

本論文的研究包括Co(por)Ar的合成和對Ar-I鍵被Co(por)活化的机理研究。首先，一系列Co(por)Ar成功的由Co(por)和取代碘帶苯在150 ℃和氫氧化鉀的作用下合成并得到中等到高的产率。 / 其次，自由能研究表明 Co(por)對Ar-I键的活化是通过碘原子轉移進行的。相对速率k[subscript rel]从取代碘代苯和碘代苯同Co(por)的競爭反應得出。自由能關係研究表明logk[subscript rel]同取代常數σp-的哈密特相关给出一斜率為1.02的直線，表明高度離域的负电荷在苯环的增加和碘原子的π電子同對位取代基在過渡態的共軛。基于这个事实和对其它机理的排除得出Co(por)對Ar-I键的活化的機理為碘原子轉移機理。因此， Co[superscript II](ttp)首先同ArI反應形成一個直線型過渡態[Co(ttp)---I---Ar]，而後生成Co(ttp)I同一個苯自由基(Ar·)。Ar同Co[superscript II](ttp)反應生成Co(ttp)Ar，Co(ttp)I同 KOH反應生成Co[superscript II](ttp)和H₂O₂，並且Co[superscript II](ttp)同ArI繼續反應。 / This research includes the synthesis of cobalt porphyrin aryl complexes (Co(por)Ar) and mechanistic study of the aryl-iodine (Ar-I) bond activation by Co(por). First, a series of cobalt porphyrin aryl complexes, Co(por)Ar, were successfully synthesized from Co(por) and aryl iodides in moderate to high yield in the presence of potassium hydroxide at 150°C. / Second, the free energy relationship study demonstrates that Ar-I bonds are activated by cobalt porphyrin (Co(por)) through an iodine atom transfer pathway. The relative rates (k[subscript rel]) were derived from competition reactions of substituted aryl iodides and phenyl iodide with Co(por). The free energy relationship study illustrates that the krel against σp - yields linear behavior with positive slope (ρ = 1.02), suggesting that a highly delocalized negative charge builds on the aryl ring, and conjugation of π-electron density of iodine atom with para substituents occurs in the transition state. With this fact and the exclusion of other possible mechanisms, it is concluded that the mechanism of activation of Ar-I bond by Co(por) involves iodine atom transfer pathway. Thus, Co[superscript II](ttp) reacts with ArI to form a linear transition state [Co(ttp)---I---Ar], which then yields Co(ttp)I and an aryl radical (Ar·). Ar· reacts with Co(ttp) to give Co(ttp)Ar, Co(ttp)I reacts with KOH to give Co[superscript II](ttp) and H₂O₂, and Co(ttp) continues to react with ArI. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Li, Chen. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2012. / Includes bibliographical references (leaves 50-55). / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstracts also in Chinese. / Table of Contents --- p.i / Acknowledgements --- p.iv / Abbreviations --- p.v / Abstract --- p.vi / Structural Abbreviations for Porphyrins --- p.ix / Chapter Chapter 1 --- General Introduction --- p.1 / Chapter 1.1 --- Application of Cobalt Porphyrin Complexes --- p.1 / Chapter 1.2 --- Energy Level Diagram for Cobalt Porphyrin Complexes --- p.1 / Chapter 1.3 --- Co(I) Porphyrin Chemistry --- p.2 / Chapter 1.4 --- Co(II) Porphyrin Chemistry --- p.3 / Chapter 1.5 --- Co(III) Porphyrin Chemistry --- p.5 / Chapter 1.6 --- Activation of Aryl Carbon-Halogen bond by Cobalt Complexes --- p.5 / Chapter 1.6.1 --- Definination of pathways of activation of aryl carbon-halogen bond by transition metals --- p.5 / Chapter 1.6.2 --- Bond dissociation energy (BDE) of Aryl halides --- p.6 / Chapter 1.6.3 --- Mechanism of aryl carbon-halogen bond activation by cobalt complex --- p.7 / Chapter 1.6.3.1 --- Oxidative addition --- p.7 / Chapter 1.6.3.2 --- Nucleophilic Aromatic Substitution --- p.8 / Chapter 1.6.3.3 --- Radical pathway --- p.9 / Chapter 1.7 --- Free energy relationship study of aryl-halide bond activation by transition metal complexes --- p.13 / Chapter 1.7.1 --- Oxidative addition of aryl-halide bond by transition metal complexes --- p.13 / Chapter 1.7.2 --- Aryl-halide bond acitvation by transition metal complexes via radical pathway --- p.18 / Chapter 1.8 --- Objectives of the work --- p.21 / Chapter Chapter 2 --- Mechanistic study of Bond Activation of Aryl Carbon-Iodide (C-I) Bonds by Cobalt(II) Porphyrin --- p.22 / Chapter 2.1 --- Background --- p.22 / Chapter 2.2 --- Aryl Carbon-iodide (C-I) bond Activation by Co(II) Porphyrins --- p.22 / Chapter 2.3 --- Preparation of Starting Materials --- p.23 / Chapter 2.3.1 --- Synthesis of Porphyrins --- p.23 / Chapter 2.3.2 --- Synthesis of Cobalt(II) Porphyrins --- p.23 / Chapter 2.4 --- Optimization of the reaction conditions --- p.24 / Chapter 2.4.1 --- Optimization of Substrate, Base and Additive --- p.24 / Chapter 2.4.2 --- Temperature Optimization --- p.24 / Chapter 2.5 --- Halogen Atoms Effect on the Cleavage Rates of Ph-X (X = Br, Cl) Bonds --- p.25 / Chapter 2.6 --- Substrate Scope of Base-Promoted Aryl C-I Activation by Co[superscript II](ttp) --- p.26 / Chapter 2.7 --- Porphyrin Scope --- p.27 / Chapter 2.8 --- X-Ray Data of Cobalt(III) Porphyrin Aryls --- p.28 / Chapter 2.9 --- Mechanistic Study of Aryl C-I Bond Activation by Co[superscript II](ttp) --- p.29 / Chapter 2.9.1 --- Possible Mechanistic Pathway --- p.29 / Chapter 2.9.2 --- Competition Reactions --- p.30 / Chapter 2.9.3 --- Free energy relationship study --- p.32 / Chapter 2.9.4 --- Mechanism discussion --- p.33 / Chapter 2.9.4.1 --- Nucleophilic Aromatic Substitution --- p.33 / Chapter 2.9.4.2 --- Oxiative Addition --- p.33 / Chapter 2.9.4.3 --- Radical ipso-Substitution --- p.34 / Chapter 2.9.4.4 --- Electron Transfer and Iodine Atom Transfer pathways --- p.34 / Chapter 2.10 --- Conclusions --- p.37 / Chapter Chapter 3 --- Experimental Section --- p.38 / References --- p.50 / Appendix --- p.56

非平面多環芳香化合物因其獨特的結構，性能和在材料科學中的應用引起了有機化學家的濃厚興趣。此論文討論了由於引入七元環或空間位阻效應而導致扭曲的多環芳香化合物，重點強調其合成，化學性質和潛在的應用。第1章介紹了常見的非平面多環芳香烴及其有代表性的兩類分子，即芳香碗和螺烯。它們分別因包含五元環或空間原子擁擠效應而偏離平面結構。本章論述了芳香碗及螺烯的合成，分子和超分子的結構及其應用。第2章詳細闡述了關於一類空間過度擁擠的庚富瓦烯衍生物的合成，表徵及順反異構化的研究。庚富瓦烯衍生物在光異構化和熱異構化過程中具有異常高的選擇性和大的分子結構變化。這些結果表明空間過度擁擠的庚富瓦烯衍生物是一類可被潛在應用為分子開關或者分子機器的化合物。第3章闡述了一種新的具有負曲率且與六苯並蔻等π電子的多環芳烴分子。向六苯並蔻（HBC）分子中引入七元環，我們得到了一種新穎的馬鞍狀大π分子。相比先前報導的[7]圈烯，該分子的具有較小的平均高斯曲率但卻有大的分子剛性。第4章闡述了另一種同六苯並蔻等π電子體系的非平面六苯並苝衍生物。空間原子的過度擁擠導致六苯並苝衍生物存在手性扭曲和反式折疊兩種構象。在升溫條件下該兩種構象之間可相互轉變並達致平衡。該結果連同進一步的熱力學和動力學研究加深了我們對六苯並苝的構象認知。手性扭曲的分子之間同時存在著面對面和邊對面的π-π相互作用，其可被用作場效應晶體管中的半導體材料。研究表明，分子彎曲的π體系在決定前線分子軌道能級和π-π相互作用中起到至關重要作用，因此在設計新的有機半導體材料時必須加以考慮。 / Non-planar polycyclic aromatic molecules are of great interests to organic chemists because of their unique structures, properties and useful applications in materials science. Detailed in this thesis are studies toward non-planar polycyclic aromatic molecules, which are forced out of planarity either by embedded seven-membered rings or by the steric strain from atom crowding, emphasizing on their synthesis, chemical properties and potential applications. / Chapter 1 introduces nonplanar polycyclic aromatic hydrocarbons (PAHs) with focus on two representative groups of non-planar PAHs, namely aromatic bowls and helicenes, which are forced out of plane by five-membered rings and atom crowding respectively. Here aromatic bowls and helicenes are reviewed in terms of synthesis, molecular and supramolecular structures as well as applications. / Chapter 2 details a comprehensive study on synthesis, characterization and syn/anti isomerism of overcrowded heptafulvalene derivatives. It was found that the heptafulvalene derivatives have achieved unusually high selectivity in both photo-isomerization and thermal isomerization. The predominance of syn isomer in the photo-isomerization has been clearly explained with DFT calculations in terms of the arrangement of the excited state and ground state potential energy surfaces. Another interesting finding is that the energy barrier of thermal syn-to-anti isomerization is directly related to the rigidity and crowdedness of the seven-membered rings. These findings suggest that overcrowded heptafulvalene derivatives are promising candidates for molecular switches and machines. In addition, a correction of the previously claimed synthesis of hexabenzooctalene is also introduced in this chapter. / Chapter 3 presents a new negatively curved polycyclic aromatic molecule that is π-isoelectronic to the well-known hexa-peri-hexabenzocoronene (HBC). Embedding a seven-membered ring into HBC leads to a novel saddle-shaped π-molecule, whose π-backbone is slightly less curved than the previously reported [7]circulene in terms of the average Gauss curvature, but surprisingly much more rigid than [7]circulene. The resulting heptagon-embedded PAH molecules not only are of theoretical interests in relation to aromaticity and curved π-orbitals but also can serve as segments, models and, in principle, synthetic precursors for graphitic carbon networks containing negative curvature, such as graphene containing heptagonal defects and toroidal carbon nanotubes / In Chapter 4, another type of curved π-molecule that has the same number of Clar's aromatic sextets as HBC is presented. Overcrowded fjord regions in novel derivatives of hexabenzoperylene (HBP) lead to both chiral twisted and anti-folded conformers, which are found to isomerize to each other at elevated temperature to reach an equilibrium. This finding along with the study on the thermodynamics and kinetics of the thermal isomerization has improved the early understandings on the conformation of HBP. It is found that the chiral twisted molecule exhibit both face-to-face and edge-to-face π-π interactions leading to a semiconducting film, which functions as the active layer in field effect transistors. The study reveals that the curvature of π-face plays a role in determining the frontier molecular orbital energy levels and π-π interactions and thus needs to be considered when one designs new organic semiconductors. / Chapter 5 is conclusion and outlook. / Detailed summary in vernacular field only. / Luo, Jiye. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2013. / Includes bibliographical references. / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstracts also in Chinese. / Abstract --- p.i / 中文摘要 --- p.iii / Acknowledgement --- p.iv / Table of Contents --- p.vi / Chapter Chapter 1 --- Introduction --- p.1 / Chapter 1.1 --- Curved PAHs with non-hexagonal rings --- p.3 / Chapter 1.1.1 --- Curved PAHs with four-membered rings --- p.3 / Chapter 1.1.2 --- Curved PAHs with five-membered rings --- p.5 / Chapter 1.1.3 --- Curved PAHs with seven-membered rings --- p.17 / Chapter 1.2 --- Curved PAHs with steric strain from atom crowding --- p.20 / Chapter 1.2.1 --- General Properties --- p.20 / Chapter 1.2.2 --- Synthetic methodologies --- p.21 / Chapter 1.2.3 --- Large PAHs containing multiple helicene structures --- p.28 / Chapter Chapter 2 --- Switching and Cyclization of Overcrowded Heptafulvalene Derivatives --- p.43 / Chapter 2.1 --- Introduction --- p.43 / Chapter 2.2 --- Results and Discussion --- p.46 / Chapter 2.3 --- Conclusion --- p.64 / Chapter 2.4 --- Experimental --- p.65 / Chapter Chapter 3 --- Heptagon-Embedded Hexabenzocoronene of Negative Curvature --- p.94 / Chapter 3.1 --- Introduction --- p.94 / Chapter 3.2 --- Results and Discussion --- p.95 / Chapter 3.3 --- Conclusion --- p.102 / Chapter 3.4 --- Experimental --- p.103 / Chapter Chapter 4 --- Hexabenzoperylene: Synthesis, twisted/anti isomerization and semiconductor applications --- p.118 / Chapter 4.1 --- Introduction --- p.118 / Chapter 4.2 --- Results and Discussion --- p.120 / Chapter 4.3 --- Conclusion --- p.134 / Chapter 4.4 --- Experimental --- p.134 / Chapter Chapter 5 --- Conclusion and Outlook --- p.153 / Appendix --- p.155