This thesis focuses on the mechanistic investigation of catalytic carbon-carbon σ-bond hydrogenation of hydrocarbons using water as the convenient hydrogen source under neutral conditions by group 9 metalloporphyrins M(por)X. [With diagram] / The benzylic carbon-carbon bond of [2.2]paracyclophane (PCP) was catalytically hydrogenated to give 4,4’-dimethylbibenzyl up to 98% yield using water with 10 mol% M(ttp)X pre-catalyst (ttp = 5,10,15,20-tetratolylporphyrinato dianion, M = Rhᴵᴵᴵ and Irᴵᴵᴵ, X = Me, Bn and ⁱPr) at 200°C in C₆D₆. Deuterium labeling experiments using D₂O supported water as the hydrogen source. Preliminary screening with Coᴵᴵ(ttp) catalyst in polar DMF solvent at 220°C also yielded the hydrogenation product selectively. The role of DMF is proposed to promote the hydrolysis of cobalt(III) porphyrin benzyl intermediates and increase the solubility of H₂O.[With diagram] / Kinetic studies on the stoichiometric benzylic CCA of PCP with Rhᴵᴵ(tmp) metalloradical (tmp = 5,10,15,20-tetramesitylporphyrinato dianion) gave the rate law as rate = k[Rhᴵᴵ(tmp)]²[PCP]. The 2ⁿᵈ order dependence on Rhᴵᴵ(tmp) radical suggests a bi-metalloradical CCA mechanism via a four-centered transition state. [With diagram] / In the iridium catalyzed system, Irᴵᴵᴵ(ttp)H was found to have promoting role in the hydrogenation process. The bi-molecular reductive elimination between Irᴵᴵᴵ(ttp)H and the CCA intermediates speeded up the hydrogenation process. It is estimated that this process gave the hydrogenated alkyl fragment 3 times faster than hydrolysis of the CCA intermediates. [With diagram] / 本論文主要探討在中性反應條件下，利用水作為一個方便的氫來源，以第9族金屬卟啉，M(por)X，催化碳氫化合物中的碳碳單鍵加氫反應的反應機制。 / 在200°C及溶有10 mol% M(ttp)X (M = Rhᴵᴵᴵ 和 Irᴵᴵᴵ，X = Me，Bn和ⁱPr) 預催化劑的氘代苯中，利用水把[2.2]二聚對二甲苯的苄基碳碳鍵進行催化加氫，生成高達98%的4,4’-二甲基聯苄(下稱PCP)。利用氘代水的氘標記實驗支持了氫的來源為水。另一方面，經過以Coᴵᴵ(ttp)催化劑進行了初步篩選後，能在220°C及DMF極性溶濟中使加氫產物選擇性地生成。DMF的作用被提議為促進鈷卟啉苄基的水解及增加了水的溶解度。 / 在進行了Rhᴵᴵ(tmp)與PCP的當量苄基碳碳鍵活化動力學實驗後，得出速率方程rate = k[Rhᴵᴵ(tmp)]²[PCP]。Rhᴵᴵ(tmp)的二級反應級數反映了一個經由四中心過渡態的雙金屬自由基碳碳鍵活化反應機制。 / 在由銥催化的系統中，發現了Irᴵᴵᴵ(ttp)H在加氫過程中的促進作用。Irᴵᴵᴵ(ttp)H與碳碳鍵活化中間體的雙分子還原消除反應把加氫過程加快。根據估計，這個雙分子還原消除反應比碳碳鍵活化中間體的水解要快3倍。 / To, Ching Tat. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2015. / Includes bibliographical references. / Abstracts also in Chinese. / Title from PDF title page (viewed on 14, September, 2016). / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only.

by Andy Kwong Shun Tse. / Thesis (M.Phil.)--Chinese University of Hong Kong, 1995. / Includes bibliographical references (leaves 53-57). / ACKNOWLEDGMENTS --- p.i / ABBREVIATIONS --- p.ii / ABSTRACT --- p.iv / CONTENTS --- p.v / Chapter Part 1: --- Serendipitous Synthesis of Cobalt(III) and Rhodium (III) Porphyrin-phosphoryls / Chapter I. --- INTRODUCTION --- p.1 / Chapter II. --- RESULTS AND DISCUSSIONS --- p.6 / Chapter III. --- CONCLUSION --- p.28 / Chapter Part 2: --- Synthesis of Rhodium(III) Porphyrin-silyls / Chapter I. --- INTRODUCTION --- p.29 / Chapter II. --- RESULTS AND DISCUSSIONS --- p.32 / Chapter III. --- CONCLUSION --- p.41 / EXPERIMENTAL --- p.42 / REFERENCES --- p.53 / APPENDIX I-III --- p.58 / LIST OF SPECTRA --- p.61 / SPECTRA --- p.62

by Xiang Zhou. / Thesis (Ph.D.)--Chinese University of Hong Kong, 1996. / Includes bibliographical references. / Acknowledgment --- p.i / Abstract --- p.ii / Abbreviations --- p.iii / Table of Contents --- p.iv-v / Chapter Chapter I --- Synthesis of β-substituted porphyrins --- p.1 / Chapter I-1 --- Introduction --- p.1 / Chapter I-1-1 --- Activation of alkanes: the biomimetic approach --- p.2 / Chapter I-1-2 --- Electronic effects in β-substituted porphyrins --- p.5 / Chapter I-1-3 --- Synthetic approach to β-substituted porphyrins --- p.7 / Chapter I-2 --- Results and discussions --- p.14 / Chapter I-2-1 --- Bromination of porphyrins at β-positions --- p.14 / Chapter I-2-2 --- Synthesis of boronic acids --- p.17 / Chapter I-2-3 --- Synthesis of β-substituted porphyrins --- p.18 / Chapter I-2-4 --- Uv spectra --- p.25 / Chapter I-2-5 --- "Crystal structures of H2TPP(Ph)4, H2TPP(Me)4， H2TPP(Tol)8 and H2TMP(Ph)8" --- p.26 / Chapter I-3 --- Conclusion --- p.43 / Chapter I-4 --- Experimental section --- p.44 / Chapter I-5 --- References --- p.58 / Chapter Chapter II --- Synthesis and Properties of Diporphyrins --- p.63 / Chapter II-1 --- Introduction --- p.63 / Chapter II-1-1 --- Linear dimers --- p.64 / Chapter II-1-2 --- Cofacial porphyrins (or strati-bisporphyrins) --- p.68 / Chapter II-1-3 --- Synthetic approach --- p.71 / Chapter II-2 --- Results and discussions --- p.73 / Chapter II-2-1 --- Synthetic strategy --- p.73 / Chapter II-2-2 --- Synthesis of diporphyrins via condensation and Suzuki cross- coupling --- p.75 / Chapter II-2-3 --- Synthesis of diporphyrins via Suzuki cross-coupling and condensation --- p.75 / Chapter II-2-4 --- Metalation of diporphyrins --- p.78 / Chapter II-2-5 --- Spectroscopy --- p.81 / Chapter II-3 --- Conclusion --- p.89 / Chapter II-4 --- Experimental section --- p.90 / Chapter II-5 --- Reference --- p.100 / Chapter Chapter III --- Novel Rhodium Porphyrin Complexes: Intermolecular Activation of Arene Carbon-Hydrogen Bond and Formation of a Nitrile-Bridged Coordination Polymer --- p.104 / Chapter III-l --- Introduction --- p.104 / Chapter III-1-1 --- Activation of C-H bonds --- p.104 / Chapter III-1-2 --- Activation of C-H bond by rhodium porphyrin complexs --- p.106 / Chapter III-2 --- Results and discussions --- p.108 / Chapter III-2-1 --- Synthesis of rhodium porphyrin complexes --- p.108 / Chapter III-2-2 --- Proton NMR --- p.112 / Chapter III-2-3 --- UV and binding studies of rhodium porphyrin complexes --- p.115 / Chapter III-2-4 --- IR spectra --- p.117 / Chapter III-2-5 --- Crystal structures of rhodium porphyrin complexes --- p.118 / Chapter III-3 --- Conclusion --- p.148 / Chapter III-4 --- Experimental section --- p.149 / Chapter III-5 --- References --- p.154 / Appendix --- p.157 / NMR Spectra --- p.159

Fong Ching-yee. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2002. / Includes bibliographical references (leaves 72-76). / Abstracts in English and Chinese. / ABSTRACT (English Version) --- p.iii / ABSTRACT (Chinese Version) --- p.v / ACKNOWLEGEMENT --- p.vi / TABLE OF CONTENTS --- p.vii / LIST OF TABLES --- p.ix / LIST OF FIGURES --- p.xi / LIST OF APPENDICES --- p.xiii / Chapter CHAPTER ONE --- Introduction / Chapter 1.1 --- Importance and Recent Development in Metalloporphyrin --- p.1 / Chapter 1.2 --- Structure of Metalloporphyrin --- p.2 / Chapter 1.3 --- General Properties of Metalloporphyrin --- p.4 / Chapter 1.4 --- Linkage Patterns of Metalloporphyrin Polymers --- p.7 / Chapter 1.5 --- Reasons for Studying Co-Por-Au Polymer --- p.10 / Chapter CHAPTER TWO --- Cobalt Porphyrin Gold (Co-Por-Au) Polymer Model / Chapter 2.1 --- Synthetic Scheme --- p.13 / Chapter 2.2 --- Experimental Results and Related Properties --- p.14 / Chapter 2.3 --- The Structure of Co-Por-Au Polymer --- p.18 / Chapter CHAPTER THREE --- Structure Characterization of Co-Por-Au Polymer by DFT Method / Chapter 3.1 --- Quantum Chemical Calculations --- p.21 / Chapter 3.2 --- Density Functional Theory --- p.22 / Chapter 3.3 --- Computational Details --- p.24 / Chapter 3.4 --- Justification for using Gaussian 98 and VASP --- p.27 / Chapter 3.5 --- Results and Discussions --- p.30 / Chapter 3.5.1 --- Monomers of TPHP and TPCNP --- p.30 / Chapter 3.5.1.1 --- The Geometry of the Monomer Structures of TPhP and TPCNP --- p.30 / Chapter 3.5.1.2 --- The Axial Coordination Mode of Monomer in TPhP and TPCNP --- p.34 / Chapter 3.5.1.3 --- Comparison between Hybrid DFT and Pure DFT method --- p.38 / Chapter 3.5.1.4 --- Comparison with Other Porphyrin System --- p.40 / Chapter 3.5.1.5 --- Summary --- p.43 / Chapter 3.5.2 --- Polymers of TPhP and TPcnP --- p.44 / Chapter 3.5.2.1 --- (μ-pyrazine)(octaethylporphyrinato)iron(II) {[Fe(OEP)pyz]}n --- p.44 / Chapter 3.5.2.2 --- Energetic Comparison of TPHP and TPCNP with Different Axial Coordination Modes --- p.46 / Chapter 3.5.2.3 --- Geometry of the Repeating Units in the Polymer of TPhP and TPCNP --- p.48 / Chapter 3.5.2.4 --- Comparison with Other Porphyrin System --- p.52 / Chapter 3.5.2.5 --- The Electronic Structures of TPHP and TPCNP --- p.55 / Chapter 3.5.2.6 --- Summary --- p.58 / Chapter CHAPTER FOUR --- Conclusion --- p.59 / APPENDIX I-III --- p.61 / REFERENCES --- p.72

No description available.

A imobilização da MeP em suportes inorgânicos permite isolar o sítio de reação prevenindo a dimerização e/ou auto-destruição oxidativa da mesma, constituindo-se num catalisador biomimético. Neste projeto foi objetivo avaliar o comportamento biomimético de manganês porfirinas, comparando sistemas imobilizadas de diferentes maneiras em sílica funcionalizada em processos de oxigenação do cicloocteno ecicloexano, incluindo metabolismo de um fármaco. A primeira etapa do projeto consistiu na obtenção dos sistemas catalíticos contendo metaloporfirinas imobilizadas em sílicas modificadas. Para isso foi sintetizada a M(4-N-Py)TFPPH2 base livre, seguida da inserção de manganês (III) e metilação obtendo-se o catalisador Mn[{M(4-N-MePy)TFPP}]2+. Foi inserido manganês também nas porifinas base livre [T(4-N-MePy)P]Cl4 e [TFPP]H2 obtidas comercialmente obtendo-se os catalisadores Mn[T(4-N-MePy)P]5+ e Mn[TFPP]+. Realizou-se a funcionalização da sílica gel com (i) grupos sulfonatofenil e propilimidazol (SiSO3-IPG); (ii) grupos 3-aminopropil (APTES); (ii) grupos 3-(2-(2-aminoetilamino) etilamino) propil (AP(EA)2TS) e (iv) cloropropil e 1,6-diaminoexano (DA1,6Si). Essas sílicas foram imobilizadas nas manganêsporfirinas através de interações eletrostáticas ou via ligação covalente. Esses catalisadores foram usados na oxigenação de (Z)-cicloocteno e cicloexano e no estudo de metabolismo oxidativo do fármaco praziquantel (agente anti-helmíntico). Os catalisadores [Mn(TFPP)]- APTES, [Mn(TFPP)]- AP(EA)2TS, [Mn{M(4-N-MePy)TFPP}]-SiSO3, [Mn{M(4-N-MePy)TFPP}]- SiSO3(IPG), [Mn{M(4-N-MePy)TFPP}]-APTES, [Mn{M(4-N-MePy)TFPP}]- AP(EA)2TS, [Mn{M(4-N-MePy)TFPP}]- DA1,6Si foram usados em reações de epoxidação do (Z)-cicloocteno pelo PhIO e os resultados obtidos foram baixos. Já com H2O2 como oxidantes os resultados foram muito bons quando foi adicionado imidazol. Nas reações de hidroxilação do cicloexano os rendimentos obtidos foram altos quando a MnP foi imobilizada por interação eletrostática. Neste sistema as oxidações competitivas são minimizadas. Os sistemas com melhores resultados foram selecionados para estudos com o praziquantel (PZQ). Diferentemente dos resultados obtidos previamente com FeP, os sistemas com MnPs se revelaram bons catalisadores biomiméticos, uma vez que apresentaram quantidades expressivas do metabólito trans-4\'-OH, o principal metabólito produzido in vivo. As MnPs, em particular as piridis substituídas apresentaram boa conversão de PZQ sendo [Mn{T(4-N-MePy)P}]-SiSO3 o melhor, além de produzir 38 % do trans-4\'-OH, apresentou 87 % de conversão. Estes resultados preliminares indicam um sistema muito promissor com resultados inéditos. / The immobilization of metalloporphyrins in inorganic supports allows to isolate reaction site preventing dimerization and/or catalyst oxidative selfdestruction constituting in a biomimetic system. In this project the aim was evaluate the biomimetic behaviour of manganese porphyrins, comparing systems immobilized on sílica in different ways in oxygenations processes of (Z)- cyclooctene and cyclohexane, including a study of drug metabolism. Initially the catalytic systems containing metaloporphyrins immobilized on modified silica were obtained. The free base M(4-N-Py)TFPPH2 was firstly synthesized, then the MnIII was inserted, methylated obtaining the catalyst Mn[{M(4-N-MePy)TFPP}]2+. The MnIII also was inserted in the commercials free base [T(4-N-MePy)P]Cl4 e [TFPP]H2 obtaining the catalysts Mn[T(4-N-MePy)P]5+ e Mn[TFPP]+. The sílica gel were functionalizated with (i) sulfonatephenyl and propylimidazole groups (SiSO3-IPG); (ii) 3-aminopropil groups (APTES); (ii) 3-(2- (2-aminoethyilamine) ethilamine) propyl groups (AP(EA)2TS) and (iv) chloropropyl e 1,6-diaminehexane (DA1,6Si). Manganese porphyrins were immobilized on these sílica supports through electrostatic interactions or covalent bond. These catalysts were used in the (Z)-ciclooctene and cyclohexane oxigenationand in the oxidative metabolism of praziquantel (antihelmintic agent). 13 The catalysts [Mn(TFPP)]- APTES, [Mn(TFPP)]- AP(EA)2TS, [Mn{M(4-NMePy) TFPP}]-SiSO3, [Mn{M(4-N-MePy)TFPP}]- SiSO3(IPG), [Mn{M(4-NMePy) TFPP}]-APTES, [Mn{M(4-N-MePy)TFPP}]- AP(EA)2TS, [Mn{M(4-NMePy) TFPP}]- DA1,6Si were used in (Z)-ciclooctene epoxidation rendering low yields using PhIO as oxidant, contrasting the good yields when imidazole and H2O2 as oxidant were used. In the hydroxylation of cyclohexane the yields were high when the MnP were immobilized through electrostatic interaction. In this system the competitive oxidations are minimized. The best systems were selected for to study the praziquantel oxidation. Differently from FeP results previously obtained, the MnP systems revealed good biomimetic catalysts for PZQ, since high amount of trans-4\'-OH metabolite was obtained, the principal in vivo metabolites. The pyridil substituted MnP, particularly [Mn{T(4-N-MePy)P}]-SiSO3 showed the best results, besides the high yield of trans-4\'-OH (38%), the convertion attained 87%. These results are inedited and very promising biomimetic catalytic systems.

Tetraphenylporphyrins can be used to absorb visible light and pass on their excitation energy to electron transfer agents. The purpose of this research has been to investigate our ability to understand and control the energetics of porphyrin derivatives in order to use their electron transfer ability to harness the energy of sunlight. Shifts in the redox (reduction and oxidation) potentials of tetraphenylporphyrins result from variations in the substituents attached at the para- position of the phenyl rings of tetraphenylporphyrins, as well as variations in the state of ionization of those substituents, and the solvent in which the reactions are carried out. To measure the effect these variations, results from cyclic voltammetric experiments were plotted versus literature values of Hammett substituent constants to confirm the validity of linear free energy relationships as a model of substituent effects. Solvent effects on reduction potentials were correlated using experimentally determined values of the empirical solvent parameter ET. Some specific conclusions are summarized. 1. The usefulness of linear free energy relationships in correlating variations in redox potentials with changes in substituent was confirmed with two exceptions. Two of the porphyrins were shown to undergo a different electrochemical oxidation mechanism than the remaining porphyrins, and another porphyrin was shown to be more difficult to reduce than predicted on the basis of its substituent constant. 2. Solvent effects, here investigated as the effect of added water on the reduction potential of tetraaminophenylporphyrin in DMSO, were demonstrated to correlate with the Dimroth-Reichardt solvent parameter, ET , determined experimentally for each water-DMSO mix. 3. Variations in the state of ionization of ionizable substituents such as carboxylic acid, amine, and hydroxyl substituents were shown to affect porphyrin electrochemistry mostly through the protonation of bulk, solution-phase porphyrin by added proton donor. An additional effect of added proton donor was noted in an alteration in the mechanism of reduction to include some of a different mechanism wherein reduced porphyrin is protonated in a chemical equilibrium and then further reduced electrochemically.

The study of cancer plays an important role in modern medical science. Over the years, a lot has been learnt about the properties and treatment of cancer cells. Despite the remarkable progress made in understanding the genesis of cancer, the work so far has had very little impact in the clinic especially the design of new and improved drugs. Platinum-based drugs such as cis-diamminedichloroplatinum(II) and its anolgue, carboplatin, are the most effective chemotherapeutic agents used in the treatment of testicular, ovarian, bladder and lung cancers. Nevertheless, the emergence of toxic side-effects compromises its clinical effectiveness. It is generally agreed that most of the toxic effects of platinum-based drugs arise from their lack of selectivity. This thesis reports on the development of new platinum(II) complexes bound to carrier molecules with the hope of obtaining compounds which display the cytotoxic effects only in tumour tissue. In addition, some information is included about what is known about the causes of cancer, how it kills and the current methods of treatment / Doctor of Philosophy (PhD)

This thesis reports the spectroscopic and computational studies of two classes of compounds, which have applications in new optoelectronic materials technology. Substituted ligands of dipyrido-[3,2a:2�,3�c]phenazine (dppz), and their Cu(I), Re(I) and Ru(II) complexes have utility in organic electroluminescent devices. A series of Zn(II) tetraphenylporphyrins with conjugated functional groups at the β-position have been used with success in liquid heterojunction dye-sensitized solar cells. The vibrational spectra and optoelectronic properties of the two classes were investigated using Raman, resonance Raman and transient resonance Raman spectroscopy, in conjunction with density functional theory methods. Density functional theory frequency calculations were used to aid vibrational mode assignments for the dppz compounds, and show close agreement with the experimental non-resonance Raman spectra. The enhancement of modes which are localized on differing sections of the ligand was identified. The nature of the absorbing chromophores for the dppz ligands and complexes was established using resonance Raman spectroscopy in concert with vibrational assignments from calculations. Transient resonance Raman spectra of the ligands provided spectral signatures for the triplet ligand-centred state; these features were observed in the TR� spectra of the metal complexes, along with other features attributable to MLCT states. Electroluminescent devices were fabricated using the dppz ligands and complexes as emissive dopants, and their properties investigated. The optoelectronic behaviour of the devices was found to be influenced by the mechanism of exciton formation on the dopant. The device properties were also dependent on the dopant concentration, the concentrations of other components and the driving voltage. The electronic structure of the porphyrin compounds was investigated using time-dependent density functional theory methods. Comparison of calculated optical transitions with experimental data shows that the calculations predict trends in the optical absorption spectra with change of functional group and with increase in conjugation chain length. The calculations suggest that the electron-withdrawing substituent decreases the configuration interaction effect by breaking the degeneracy of the two lowest unoccupied MOs, and other configuration interaction effects come into play involving other frontier MOs. Interrupting the conjugation of the functional group is shown to mitigate the breakdown of the configuration interaction. The perturbation of the normal electronic structure of the porphyrin by the substituent was also investigated using resonance Raman spectroscopy. Vibrational analysis identified bands due to the substituent, implying coupling between the porphyrin and substituent chromophores. Changes in frequency of porphyrin core modes due to the differing substituents and different metal centres were reproduced by density functional theory calculations. This project has allowed the spectroscopic investigation of the active optical states in a number of polypyridyl and porphyrin compounds, and determined the efficacy of DFT and TDDFT calculations to predict the properties of these compounds.

Anion Binding has recently emerged as an important field of study due to the role these small inorganic species play in a plethora of biological processes. Chapter 1 of this thesis describes the biological relevance and scientific justifications for studying the ability of synthetic molecules to transport or extract anions under interfacial conditions. This chapter also serves to underscore the need to study both the thermodynamics and kinetics of anion binding as achieved using synthetic receptors. Methods for determining the thermodynamics of ion recognition are well-developed, and many equilibrium analyses of supramolecular binding events have been reported; however, the kinetics of such interactions are often neglected. Chapter 2 details the author's efforts to address this deficiency with respect to anion-binding and reports progress towards quantitative kinetic analyses of the interaction between cyclo[8]pyrrole (C8), an expanded porphyrin, and two test anions. It has been determined that stopped-flow analysis can provide on and off-rates, as well as activation parameters not accessible through thermodynamic means. Initial flash photolysis kinetic studies have also revealed that C8 has the potential to act as a photosensitizing agent through electron donation. This work is presented in Chapter 3, wherein the author discusses the construction of novel donor-acceptor dyads based on C8. As detailed in this chapter, time-resolved optical analyses have confirmed that photoinduced electron transfer occurs under conditions of photoexcitation and that the lifetime of the charge separated state is approximately 300 [mu]s. Finally, Chapter 4 describes a comprehensive set of spectroscopic work conducted by the author involving porphyrin and porphycenes that have a RuCp* (Cp*: pentamethylcyclopentadienyl) fragment either coordinated to the central porphyrinic core or directly attached to the "[pi]-face" of the macrocycle. These systems display unique intramolecular electron transfer properties that are ascribed to the metallated-porphyrin core acting as an electron acceptor, as opposed to a donor as is normally observed with porphyrins. / text