published_or_final_version / abstract / Chemistry / Doctoral / Doctor of Philosophy

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by Ka Lok Cheng. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2000. / Includes bibliographical references (leaves 115-122). / Abstracts in English and Chinese. / Abstract --- p.i / Abstract (in Chinese) --- p.ii / Acknowledgement --- p.iii / Table of Contents --- p.iv / List of Figures --- p.viii / List of Tables --- p.xi / Abbreviations --- p.xii / Chapter PART I --- SYNTHESIS OF FERROCENE-CONTAINING PUSH-PULL DIPHENYLPORPHYRINS --- p.1 / Chapter Chapter 1 --- Introduction --- p.2 / Chapter 1.1 --- Introduction to Nonlinear Optics --- p.2 / Chapter 1.1.1 --- Interactions of Light with Matters --- p.2 / Chapter 1.1.2 --- Structural Requirements of Second-Harmonic Generating Molecules --- p.4 / Chapter 1.2 --- Ferrocene as an Electron Donor in Second Harmonic Generating Molecules --- p.7 / Chapter 1.3 --- Porphyrin as a Platform of Second Harmonic Generating Molecules --- p.16 / Chapter 1.4 --- Target Molecules of this Project --- p.22 / Chapter Chapter 2 --- Result and Discussion --- p.23 / Chapter 2.1 --- Preparation of Alkynyl Fragments --- p.23 / Chapter 2.1.1 --- Preparation of 2-ferrocenylethyne (24) --- p.23 / Chapter 2.1.2 --- Preparation of 1 -ethynyl-4-nitrobenzene (26) --- p.24 / Chapter 2.1.3 --- "Preparation of l-ethynyl-4-(N,N-dimethylaminophenyl) benzene (28)" --- p.25 / Chapter 2.2 --- Preparation of Porphyrin Precursors --- p.26 / Chapter 2.3 --- "Synthesis and Characterizations of 5-(2'-Ferrocenylethynyl)-l5- formyl-10,20-diphenylporphyrinatonickel(II) (36)" --- p.29 / Chapter 2.4 --- "Synthesis and Characterizations of 5-(2',2'-Dicyanoethenyl)-l5- (2""-Ferrocenylethynyl)-10,20-diphenylporphyrinatonickel(II) (38)" --- p.33 / Chapter 2.5 --- "Synthesis and Characterizations of 5-Ferrocenylethynyl-l 5-(4""- nitrophenylethynyl)-10,20-diphenylporphyrinatonickel(II) (40)" --- p.37 / Chapter 2.6 --- "Synthesis and Characterizations of 5-Ferrocenylethynyl-l 5-(4'- (N,N-dimethylamino)phenyl)ethynyl)-10,20-diphenyl porphyrinatonickel(II) (47)" --- p.43 / Chapter 2.7 --- Conclusion for Part One --- p.47 / Chapter Chapter 3 --- Experimental Section --- p.48 / Chapter 3.1 --- General Information --- p.48 / Chapter 3.2 --- Physical Measurements --- p.48 / Chapter 3.3 --- Preparation of Alkynyl Fragments --- p.49 / Chapter 3.4 --- Preparation of Some Known Porphyrins --- p.54 / Chapter 3.5 --- "Synthesis of Ferrocenyl ""Push-pull"" Porphyrin" --- p.58 / Chapter PART II --- LIGHT-HARVESTING NAPHTHALENE-PHTHALOCYANINE SYSTEMS --- p.65 / Chapter Chapter 4 --- Introduction --- p.55 / Chapter 4.1 --- Porphyrin-based Light-harvesting systems --- p.66 / Chapter 4.1.1 --- Multiporphyrins --- p.57 / Chapter 4.1.2 --- Carotenoid-porphyrins --- p.74 / Chapter 4.1.3 --- Boron-dipyrrin porphyrins --- p.75 / Chapter 4.1.4 --- Anthracene-porphyrin systems --- p.73 / Chapter 4.1.5 --- Dendritic porphyrins --- p.79 / Chapter 4.2 --- Phthalocyanine-based Light-harvesting systems --- p.80 / Chapter 4.3 --- Objective of this project --- p.83 / Chapter Chapter 5 --- Result and Discussion --- p.84 / Chapter 5.1 --- Preparation of naphthalene-phthalocyanine systems --- p.84 / Chapter 5.1.1 --- Synthesis of zinc(II) tetra( 1 -naphthoxy)phthalocyanines --- p.84 / Chapter 5.1.2 --- Synthesis of tetra[2-(l´ة-naphthoxy)ethoxy] phthalocyaninatozinc(II) (83) --- p.85 / Chapter 5.1.3 --- "Synthesis of 2,3,9,10,16,17,23,24-octa( 1 -naphthoxy) phthalocyaninatozinc(II) (89)" --- p.86 / Chapter 5.2 --- Absorption spectra of naphthalene-phthalocyanine systems --- p.88 / Chapter 5.2.1 --- Absorption spectra at different concentrations --- p.89 / Chapter 5.2.2 --- Comparison of the absorption spectra of the naphthoxy phthalocyanine with the spectra of the mixture of corresponding 1-ethoxynaphthalene and alkoxyphthalocyanines --- p.92 / Chapter 5.3 --- Fluorescence Quantum yields of Naphthalene-Phthalocyanine Systems --- p.96 / Chapter 5.4 --- Singlet-singlet energy transfer efficiencies of Naphthalene- phthalocyanine Systems --- p.98 / Chapter 5.4.1 --- Methodology --- p.98 / Chapter 5.4.2 --- Determination of energy transfer quantum yields --- p.99 / Chapter 5.5 --- Conclusion for Part II --- p.103 / Chapter Chapter 6 --- Experimental Section --- p.104 / Chapter 6.1 --- General Information --- p.104 / Chapter 6.2 --- Synthesis of tetra( 1 -naphthoxy)phthalocyanines --- p.105 / Chapter 6.3 --- Synthesis of tetra(naphthoxyethoxy)phthalocyanine --- p.108 / Chapter 6.4 --- Synthesis of octa( 1 -naphthoxy)phthalocyanine --- p.111 / References --- p.115 / Appendix A: Spectra of new compounds not discussed in the main text --- p.123 / Appendix B: X-ray crystallographic data of compound40 --- p.133

Thesis (Ph.D.)--Massachusetts Institute of Technology, Dept. of Chemical Engineering, 1979. / MICROFICHE COPY AVAILABLE IN ARCHIVES AND SCIENCE. / Bibliography: leaves 252-265. / Ph.D.

本論文主要研究了鹼性添加劑促進二價鈷卟啉絡合物(Co{U+1D35}{U+1D35}(por))在苯溶劑中與溴代苯及其衍生物(ArX)的反應及鹼性條件下，該絡合物催化溴代苯及其衍生物的脫鹵反應。 / 第一部分主要介紹了在KOH和{U+1D57}BuOH存在下，Co{U+1D35}{U+1D35}(por)斷裂碳-溴鍵（Ar-Br）形成各種三價鈷卟啉芳基絡合物（Co{U+1D35}{U+1D35}{U+1D35}(por)Ar）(eq. 1)。 / 機理研究顯示，Co{U+1D35}{U+1D35}(por)首先從ArBr中得到Br·形成芳基自由基（Ar·）及Co{U+1D35}{U+1D35}{U+1D35}(por)Br (Scheme 1, i). Ar 與另一個Co{U+1D35}{U+1D35}(por)反應得到Co{U+1D35}{U+1D35}{U+1D35}(por)Ar (Scheme 1, ii)。在鹼性條件中，Co{U+1D35}{U+1D35}{U+1D35}(por)Br 最終形成CoII(por)從而繼續反應 (Scheme 1, iii-iv)。 / 第二部份主要介紹了在200 ºC時， 鹼性條件下Co{U+1D35}{U+1D35}(por)催化鹵代苯及其衍生物脫鹵形成對應芳烴的反應 (eq. 2)。 該反應在四氫呋喃（THF）及異丙醇 ({U+2071}PrOH) 中都可以進行。 / 機理研究顯示， Co{U+1D35}{U+1D35}(ttp) 首先與ArBr反應得到Ar· 和Co{U+1D35}{U+1D35}{U+1D35}(ttp)Br (Scheme 2, i)。 Ar 從溶劑（THF 或者 {U+2071}PrOH）得到一個氫原子從而形成芳烴 (ArH) (Scheme 2, ii)。 Ar 也可以與另一個Co{U+1D35}{U+1D35}(ttp) 反應得到Co{U+1D35}{U+1D35}{U+1D35}(ttp)Ar。 在鹼性條件下， Co{U+1D35}{U+1D35}{U+1D35}(ttp)Ar水解形成ArH 和 Co{U+1D35}{U+1D35}{U+1D35}(ttp)OH (Scheme 2, iii)。 Co{U+1D35}{U+1D35}{U+1D35}(ttp)Br 與KOH進行取代反應得到Co{U+1D35}{U+1D35}{U+1D35}(ttp)OH, 并最終形成催化劑Co{U+1D35}{U+1D35}(ttp) (Scheme 1, iii-iv)。所以， 溶劑 （THF 或者 {U+2071}PrOH）及H₂O 都可以作為Co{U+1D35}{U+1D35}(ttp) 催化鹵代苯脫鹵形成芳烴的氫的來源。 / This thesis focuses on (1) the base-promoted aryl bromine bond (Ar-Br) cleavages by cobalt(II) porphyrins and (2) catalytic hydrodehalogenation of aryl bromides by cobalt(II) porphyrin in alkaline conditions. / Part I describes the aryl bromine bond cleavage with cobalt(II) porphyrin (Co{U+1D35}{U+1D35}(por)) in the presence of KOH and {U+1D57}BuOH in benzene at 150ºC to give cobalt(III) porphyrin aryls (Co{U+1D35}{U+1D35}{U+1D35}(por)Ar) (eq. 1). / [With images] / Mechanistic studies suggest that CoII(por) first abstracts the bromine atom from the aryl bromide to form aryl radical (Ar) and Co{U+1D35}{U+1D35}{U+1D35}(por)Br (Scheme 1, i). Ar· further reacts with Co{U+1D35}{U+1D35}(por) to generate Co{U+1D35}{U+1D35}{U+1D35}(por)Ar (Scheme 1, ii). Co{U+1D35}{U+1D35}{U+1D35}(por)Br undergoes ligand substitution with KOH to form Co{U+1D35}{U+1D35}{U+1D35}(por)OH, which quickly gives Co{U+1D35}{U+1D35}(por) and H₂O₂ (Scheme 1, iii). H₂O₂ undergoes base-promoted decomposition to form H₂O and O₂ (Scheme 1, iv). / [With images] / Scheme 1 Reaction Mechanism of Base-promoted Ar-Br Cleavage with Co{U+1D35}{U+1D35}(por) / Part II describes the catalytic hydrodehalogenation of aryl bromides by Co{U+1D35}{U+1D35}(ttp) at 200 ºC in alkaline conditions to generate arenes (eq. 2). The reaction can occur in both THF and {U+2071}PrOH. / [With images] / Mechanistic studies suggest that Co{U+1D35}{U+1D35}(ttp) also first abstracts the bromine atom from the aryl bromide in the presence of KOH to form Ar· and Co{U+1D35}{U+1D35}{U+1D35}(ttp)Br (Scheme 2, i). Ar· can abstract a hydrogen atom from the solvent (THF or {U+2071}PrOH) to form arenes (Scheme 2, ii). Ar also could be trapped by Co{U+1D35}{U+1D35}(ttp) to give Co{U+1D35}{U+1D35}{U+1D35}(ttp)Ar, which undergoes hydrolysis in the presence of OH⁻ to the arene (ArH) and Co{U+1D35}{U+1D35}{U+1D35}(ttp)OH (Scheme 2, iii). Co{U+1D35}{U+1D35}{U+1D35}(ttp)Br gives Co{U+1D35}{U+1D35}{U+1D35}(ttp)OH by ligand substitution with KOH and Co{U+1D35}{U+1D35}{U+1D35}(ttp)OH regenerates the catalyst Co{U+1D35}{U+1D35}(ttp) (Scheme 1, iii-iv). The solvent (THF or {U+2071}PrOH) and H₂O are the hydrogen sources for the catalytic dehalogenation of aryl bromides by Co{U+1D35}{U+1D35}(ttp). / Scheme 2 Mechanism of Catalytic Dehalogentaion of ArBr by CoII(ttp) in Alkaline Media / 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. / Liu, Chunran. / "October 2012." / Thesis (M.Phil.)--Chinese University of Hong Kong, 2013. / Includes bibliographical references (leaves ). / Abstracts also in Chinese. / Chapter Table of Contents --- p.i / Chapter Acknowledgements --- p.iv / Chapter Abbreviations --- p.v / Chapter Abstract --- p.vi / Chapter Part I --- The Base-promoted Aryl Bromine Bond Cleavage of Aryl Bromides by Cobalt(II) Porphyrins / Chapter Chapter 1 --- General Introduction --- p.1 / Chapter 1.1 --- Introduction to Porphyrins and Group 9 metalloporphyrins --- p.1 / Chapter 1.1.1 --- Porphyrin Ligand --- p.1 / Chapter 1.1.2 --- Group 9 metalloporphyrins --- p.2 / Chapter 1.1.3 --- Chemistry of Group 9 Metalloporphyrin --- p.3 / Chapter 1.1.3.1 --- Chemsitry of M{U+1D35}(por) --- p.3 / Chapter 1.1.3.2 --- Chemsitry of M{U+1D35}{U+1D35}(por) --- p.4 / Chapter 1.1.3.3 --- Chemsitry of M{U+1D35}{U+1D35}{U+1D35}{U+1D35}(por) --- p.4 / Chapter 1.1.3.4 --- Chemsitry of M{U+1D35}{U+1D35}{U+1D35}{U+1D35}(por)OH --- p.6 / Chapter 1.2 --- Physical Properties of Aryl Halides --- p.9 / Chapter 1.3 --- Synthesis of Metalloporphyrin Aryl --- p.10 / Chapter 1.4 --- Modes of Reactivity of Aryl Carbon-Halogen Bond Cleavage by Transition Metal Complexes --- p.11 / Chapter 1.4.1 --- Oxidative Addition (OA) --- p.11 / Chapter 1.4.2 --- Nucleophilic Aromatic Substitution (SNA) --- p.14 / Chapter 1.4.3 --- Halogen Atom Transfer (HXA) --- p.14 / Chapter 1.4.4 --- Radical ipso-Substitution --- p.15 / Chapter 1.5 --- Scope of Part I --- p.16 / Chapter Chapter 2 --- Base-promoted Aryl Bromine Bond Cleavage of Aryl Bromides by Cobalt(II) Porphyrins / Chapter 2.1 --- Introduction --- p.17 / Chapter 2.2 --- Objectives of the Work --- p.18 / Chapter 2.3 --- Preparation of Starting Materials --- p.18 / Chapter 2.3.1 --- Synthesis of Porphyrin --- p.18 / Chapter 2.3.2 --- Synthesis of Cobalt(II) Porphyrin --- p.18 / Chapter 2.3.3 --- Synthesis of Co{U+1D35}{U+1D35}{U+1D35}(ttp)Br --- p.19 / Chapter 2.4 --- Discovery of Ph-Br Bond Cleavage by Co{U+1D35}{U+1D35}(ttp) with KOH --- p.19 / Chapter 2.5 --- Optimization of Reaction Conditions --- p.20 / Chapter 2.5.1 --- {U+1D57}BuOH Effect --- p.20 / Chapter 2.5.2 --- Solvent Effect --- p.21 / Chapter 2.5.3 --- Temperature Effect --- p.21 / Chapter 2.5.4 --- Base Loading Effect --- p.22 / Chapter 2.6 --- Summary of Optimization of the Base-promoted Ph-Br Bond Cleavage by Co{U+1D35}{U+1D35}(ttp) --- p.22 / Chapter 2.7 --- Porphyrin Ligand Effect --- p.23 / Chapter 2.8 --- Substrate Scope of Aryl Bromides --- p.24 / Chapter 2.9 --- Mechanistic Studies --- p.25 / Chapter 2.9.1 --- Possible Pathways of Ar-Br Bond Cleavage --- p.25 / Chapter 2.9.1.1 --- Oxidative Addition (OA) --- p.26 / Chapter 2.9.1.2 --- Nucleophilic Aromatic Substitution (SNA) --- p.27 / Chapter 2.9.1.3 --- Radical ipso-Substitution --- p.28 / Chapter 2.9.1.4 --- Halogen Atom Transfer (HXA) --- p.28 / Chapter 2.9.2 --- Electronic Effect of 4-Substituted ArBr by Hammett Plot --- p.29 / Chapter 2.9.3 --- Proposed Mechanism --- p.32 / Chapter 2.9.4 --- Evidence for Halogen Atom Transfer --- p.33 / Chapter 2.10 --- Conclusion --- p.35 / Chapter Chapter 3 --- Experimental Section --- p.36 / Reference --- p.53 / Chapter Part II --- Catalytic Hydrodehalogenation of Aryl Bromides by Cobalt(II) Porphyrin in Alkaline Conditions / Chapter Chapter 4 --- General Introduction --- p.58 / Chapter 4.1 --- Introduction --- p.58 / Chapter 4.1.1 --- Properties of Halogenated Aromatic Compounds --- p.58 / Chapter 4.1.2 --- Reactivity of Aryl Carbon-Halogen Bond --- p.59 / Chapter 4.2 --- Hydrodehalogenation of Aryl Halides by Transiton Metal Complexes --- p.59 / Chapter 4.2.1 --- Molecular Hydrogen (H₂) --- p.60 / Chapter 4.2.2 --- Alcohols and Metal Alkoxides --- p.61 / Chapter 4.2.3 --- Dimethyformamide (DMF) --- p.64 / Chapter 4.2.4 --- Hydrazine (NH₂-NH₂) --- p.65 / Chapter 4.2.5 --- Metal Hydrides --- p.65 / Chapter 4.2.6 --- Alkyl Grignard Reagents --- p.67 / Chapter 4.2.7 --- Formic Acid and Its Salts --- p.67 / Chapter 4.3 --- Common Reducing Agents --- p.69 / Chapter 4.3 --- Scope of Part II --- p.69 / Chapter Chapter 5 --- Catalytic Hydrodehalogenation of Aryl Bromides by Cobalt(II) Porphyrin in Alkaline Conditions / Chapter 5.1 --- Introduction --- p.70 / Chapter 5.2 --- Objectives of the Work --- p.71 / Chapter 5.3 --- Optimization of Reaction Conditions --- p.71 / Chapter 5.3.1 --- Solvent Effect --- p.71 / Chapter 5.3.2 --- Temperature Effect --- p.72 / Chapter 5.3.3 --- Base Loading Effect --- p.73 / Chapter 5.3.4 --- Porphyrin Loading Effect --- p.73 / Chapter 5.3.5 --- Atmosphere Effect --- p.74 / Chapter 5.4 --- Summary of Optimization of Hydrodehalogention of Aryl Bromides by Co{U+1D35}{U+1D35}(ttp) --- p.74 / Chapter 5.5 --- Substrate Scope of Aryl Bromides --- p.75 / Chapter 5.5.1 --- THF as the Solvent --- p.75 / Chapter 5.5.2 --- {U+2071}PrOH as the Solvent --- p.76 / Chapter 5.6 --- Catalytic Reactivity of Co{U+1D35}{U+1D35}(ttp) as the Catalyst --- p.77 / Chapter 5.7 --- Mechanistic Studies --- p.78 / Chapter 5.7.1 --- Proposed Mechanism of Hydrodehalogenation of Aryl Bromides by Co{U+1D35}{U+1D35}(ttp) --- p.78 / Chapter 5.7.2 --- Hydrogen Source Investigation --- p.80 / Chapter 5.8 --- Conclusion --- p.83 / Chapter Chapter 6 --- Experimental Section --- p.84 / Reference --- p.92 / Chapter Appendix --- Appendix I --- p.101 / Appendix II --- p.112 / Appendix III --- p.118

by Marco Ming Yeung. / Thesis (M.Phil.)--Chinese University of Hong Kong, 1997. / Includes bibliographical references (leaves 90-96). / ACKNOWLEDGMENTS --- p.i / ABSTRACT --- p.ii / CONTENTS --- p.iii / LIST OF FIGURES --- p.v / LIST OF TABLES --- p.vi / ABBREVIATIONS --- p.vii / Chapter 1. --- INTRODUCTION --- p.1 / Chapter 1.1. --- Theoretical Background of Nonlinear Optics --- p.1 / Chapter 1.2. --- Organic Nonlinear Optical Chromophores --- p.5 / Chapter 1.3. --- Porphyrins as Nonlinear Optical Chromophores --- p.8 / Chapter 1.4. --- Synthetic Aspects of Porphyrins --- p.16 / Chapter 1.4.1. --- Porphyrin Substrates --- p.16 / Chapter 1.4.2. --- Vilsmeier Formylation --- p.17 / Chapter 1.4.3. --- Bromination --- p.21 / Chapter 1.4.4. --- Knoevenagel Condensation --- p.24 / Chapter 1.4.5. --- Palladium-mediated Cross-coupling --- p.25 / Chapter 2. --- RESULTS AND DISCUSSION --- p.28 / Chapter 2.1. --- "Preparation of 5,15-Diphenylporphyrinatonickel(II)" --- p.28 / Chapter 2.2. --- "Vilsmeier Formylation of 5,15-Diphenylporphyrinatonickel(II)" --- p.30 / Chapter 2.3. --- Preparation of Push-pull Porphyrins --- p.47 / Chapter 2.4. --- Molecular Structures of 65 and76 --- p.59 / Chapter 2.5. --- Nonlinear Optical Properties of Push-pull Porphyrins 65 and66 --- p.63 / Chapter 2.6. --- Attempted Syntheses of Push-pull Porphyrin Trimer and Dimer --- p.65 / Chapter 2.7. --- Conclusion --- p.69 / Chapter 3. --- EXPERIMENTAL SECTION --- p.70 / Chapter 3.1. --- General Methods --- p.70 / Chapter 3.2. --- Physical Measurements --- p.70 / Chapter 3.3. --- Preparation of Push-pull Porphyrins --- p.71 / Chapter 3.4. --- Attempted Preparation of Push-pull Porphyrin Trimer and Dimer --- p.86 / Chapter 4. --- REFERENCES --- p.90 / APPENDIX A 1 H NMR Spectra of Porphyrins --- p.97 / APPENDIX B Crystal Data for 65 and 76 --- p.115 / APPENDIX C Computed Geometry of 65 and 66 from Semiempirical PM3(tm) Calculations --- p.131

Thesis (Ph. D.)--University of Hong Kong, 2006. / Title proper from title frame. Also available in printed format.

Thesis (Ph. D.)--University of Hong Kong, 2006. / Title proper from title frame. Also available in printed format.

No description available.

No description available.