by Wing-Fong Law. / Year shown on spine: 1997. / The "2" in the title is subscript. / Thesis (M.Phil.)--Chinese University of Hong Kong, 1996. / Includes bibliographical references (leaves 103-110). / ACKNOWLEDGMENT --- p.i / CONTENTS --- p.ii / LIST OF FIGURES --- p.v / LIST OF TABLES --- p.vii / ABBREVIATIONS --- p.viii / ABSTRACT --- p.x / Chapter I. --- STUDIES OF OCTASUBSTITUTED OXO(PHTHALOCYANINATO) TITANIUM(IV) COMPLEXES / Chapter 1. --- INTRODUCTION --- p.2 / Chapter 2. --- RESULTS AND DISCUSSION / Chapter 2.1. --- Preparation of Substituted Dicyanobenzenes and Dicyanonaphthalene --- p.9 / Chapter 2.2. --- Synthesis of Octasubstituted Oxo(phthalocyaninato)titanium(IV) and (Naphthalocyaninato)oxotitanium(IV) Complexes --- p.12 / Chapter 2.3. --- "Solvent Effects on the UV-Vis Absorption Spectra of (2,3,9,10,16, 17,23,24-Octaheptylphthalocyaninato)oxotitanium(IV)" --- p.27 / Chapter 2.4. --- Aggregation of Octasubstituted Oxo(phthalocyaninato)titanium(IV) and (Naphthalocyaninato)oxotitanium(IV) Complexes --- p.29 / Chapter 2.5. --- Electrochemical Studies of Octasubstituted Oxo(phthalocyaninato)- titanium(IV) and (Naphthalocyaninato)oxotitanium(IV) Complexes --- p.34 / Chapter 2.6. --- Reactions of Disubstituted Dicyanobenzenes with Zirconium(IV) Butoxide and Urea --- p.39 / Chapter 2.7. --- Conclusion --- p.40 / Chapter 3. --- EXPERIMENTAL SECTION / Chapter 3.1. --- Materials --- p.42 / Chapter 3.2. --- Physical Measurements --- p.42 / Chapter 3.3. --- "Preparation of l,2-Dicyano-4,5-diheptylbenzene" --- p.43 / Chapter 3.4. --- "Preparation of l,2-Dicyano-4,5-bis(pentyloxy)benzene" --- p.45 / Chapter 3.5. --- "Preparation of l,2-Dicyano-4,5-bis(alkoxymethyl)benzene" --- p.47 / Chapter 3.6. --- "Preparation of 3,6-Bis(butyloxy)-l,2-dicyanobenzene" --- p.49 / Chapter 3.7. --- "Preparation of 2,3-Dicyano-5,8-dihexylnaphthalene" --- p.50 / Chapter 3.8. --- Preparation of Octasubstituted Oxo(phthalocyaninato)titanium(IV) Complexes --- p.52 / Chapter 3.9. --- Preparation of Octasubstituted (Naphthalocyaninato)oxotitanium(IV) Complex --- p.57 / Chapter 3.10. --- Miscellaneous Syntheses --- p.58 / Chapter II. --- dioxotungsten(vi) complexes with n202 and n2s2 tetradentate ligands / Chapter 1. --- INTRODUCTION --- p.62 / Chapter 2. --- RESULTS AND DISCUSSION / Chapter 2.1. --- Preparation of Tetradentate Ligands --- p.75 / Chapter 2.2. --- Preparation of Dioxotungsten(VI) Complexes --- p.78 / Chapter 2.3. --- Electrochemical Studies of Dioxotungsten(VI) Complexes --- p.86 / Chapter 2.4. --- Oxo-transfer Properties of Dioxotungsten(VI) Complexes --- p.91 / Chapter 2.5. --- Conclusion --- p.94 / Chapter 3. --- EXPERIMENTAL SECTION / Chapter 3.1. --- Materials --- p.95 / Chapter 3.2. --- Physical Measurements --- p.95 / Chapter 3.3. --- Preparation of Tetradentate Ligands --- p.96 / Chapter 3.4. --- Preparation of Dioxotungsten(VI) Complexes --- p.100 / REFERENCES --- p.103 / APPENDIX A lH NMR spectra of Pc'TiOs --- p.111 / APPENDIX B 13C{1H} NMR spectra of octasubstituted PcTi compounds --- p.113 / APPENDIX C Mass spectra of octasubstituted PcTi and PcZr compounds --- p.118 / "APPENDIX D IR spectra of octasubstituted PcTi, NcTi and PcZr compounds" --- p.124 / APPENDIX E Cyclic voltammograms of octasubstituted PcTiOs and NcTiO --- p.131 / APPENDIX F Determination of aggregation number (n) and aggregation constant (K) --- p.136 / APPENDIX G 1H NMR spectra of dioxotungsten(VI) complexes --- p.138 / APPENDIX H 13C{1H} NMR spectra of dioxotungsten(VI) complexes --- p.140 / APPENDIX I LSI mass spectra of dioxotungsten(VI) complexes --- p.143 / APPENDIX J IR spectra of dioxotungsten(VI) complexes --- p.147 / APPENDIX K Crystallographic data of W02(L2-N202) (64) --- p.150 / APPENDIX L Kinetic data for the oxo-transfer reactions --- p.160

Le développement de nouveaux matériaux luminescent pour les LEDs du futur, qui ont pour objectifs de préserver l’environnement et de réduire les dépenses énergétiques, est un thème de recherche d’actualité et un défi extrêmement intéressant pour de nombreux chercheurs. Actuellement, la plupart des LEDs commerciales sont des matériaux dopés aux lanthanides. Cependant, la situation économique et politique actuel est telle que pour l’approvisionnement en lanthanides, les pays européens sont dépendant des pays asiatiques qui ont le monopole sur la production et l’exportation des ceux-ci. Dans ce contexte, mes travaux de thèses effectués en collaboration avec l’UCCS de Lille (France) et l’Université de Siegen en Allemagne ont pour objectifs d’étudier les propriétés photoluminescentes de nouveaux oxydes ou oxohalogénures de Bismuth (sans lanthanides) étudiés préalablement par l’UCCS pour leurs caractéristiques structurales. Dans les phases sélectionnées, la connectivité des tétraèdres oxo-centrés O(BiM)4 est un paramètre clé permettant de jouer sur les propriétés optiques en changeant de polytype ou de composition chimique. De ce fait, un des objectifs de cette thèse est de déterminer les paramètres importants permettant de façonner les propriétés optiques de Bi3+ sur des bases de simples concepts tels que la connectivité du Bi, la stéréo-activité de sa paire d’électrons libres ou les structures électroniques…etc. L’étude des familles BiM2XO6 (M=Mg, Cd, Zn et X= P, As, V) et ABiO2X (A=Ca, Cd, Sr, Ba et X=Cl, Br) qui possèdent une émission intense à température ambiante valident la pertinence de ces travaux. / The development of luminescent materials for future LEDs is currently a hot-topic with respect to energy saving materials and it is an interesting challenge for many researchers to find the luminescent materials of tomorrow. Most of the current commercial LEDs are based on lanthanide activators. The economic and political context leads the European countries to be dependent on the Asian monopole, in terms of the production and exportation of lanthanides. In this context, my PhD work developed in collaboration with the UCCS at Lille, France and the University of Siegen, Germany, deals with the photoluminescence properties of some novel Bi3+ oxo-salts phosphors (lanthanide free) studied so far by the french partner for their structural aspects. In the selected phases, one key-parameter is the degree of connectivity between oxo-centered O(Bi,M)4 tetrahedra, which allows a fine tuning of optical properties from one polytype to another one and tuning the chemical composition. Therefore, one goal of this work concerns the deduction of the important parameters tailoring the Bi3+ optical properties, on the basis of simple concepts, e.g. Bi bonding scheme, Bi3+ lone pair (LP) stereo-activity, electronic structures … etc. The investigation of the BiM2XO6 (M/M´=Mg, Cd, Zn and X=P, As, V) and ABiO2X (A=Ca, Cd, Sr, Ba and X=Cl, Br) families validated the pertinence of this study, leading to bright luminescence at room temperature.

The 12-oxo-phytodienoic acid reductases (OPRs) are enzymes of the octadecanoid pathway which converts linolenic acid to a phytohormone, jasmonic acid. Bioinformatics analysis of ESTs and genomic sequences from available private and public databases revealed that the maize genome encodes eight different OPR genes. This number of maize OPR genes has been independently confirmed by Southern blot analysis and by mapping of individual OPR genes to maize chromosomes using oat maize chromosome addition lines. Survey of massively parallel signature sequencing (MPSS) assays revealed that transcripts of each OPR gene accumulate differentially in diverse organs of maize plants. This data suggested that individual OPR genes may have a distinct function in development. Similarly, RNA blot analysis revealed that distinct OPR genes are differentially regulated in response to stress hormones, wounding or pathogen infection. ZmOPR1 and ZmOPR2 appear to have important functions in defense responses to pathogens because they are transiently induced by salicylic acid (SA), chitooligosaccharides and by infection with Cochliobolus carbonum, Bipolaris maydis and Fusarium verticillioides and not by wounding. In contrast to these two genes, ZmOPR6 and ZmOPR7/8 are highly induced by wounding and treatments with wound-associated signaling molecules jasmonic acid, ethylene and abscisic acid. ZmOPR6 and ZmOPR7/8 are not induced by SA treatments or pathogen infections suggesting their specific involvement in wound-induced defense responses. Possible functions of specific OPR genes are discussed.

Thesis (M. Phil.)--University of Hong Kong, 2002. / Includes bibliographical references (leaves 180-181).

Thesis (Ph. D.)--University of Hong Kong, 1989. / Also availalbe in microfilm.

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

Proefschrift Universiteit van Amsterdam. / Met lit. opg. - Met samenvatting in het Nederlands.

Thesis (M.S.)--Duquesne University, 2003. / Title from document title page. Abstract included in electronic submission form. Includes bibliographical references (p. 117-131).

Thesis (Ph. D.)--University of Hong Kong, 1998. / Includes bibliographical references.

Thesis (M.Phil.)--University of Hong Kong, 2002. / Includes bibliographical references (leaves 180-181) Also available in print.