by Cheung Siu-shing. / Includes bibliographical references / Thesis (M.Ph.)--Chinese University of Hong Kong, 1986

Kam-Hung Low. / Thesis submitted in: December 2003. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2004. / Includes bibliographical references. / Abstracts in English and Chinese. / Table of contents --- p.i. / Acknowledgements --- p.vi. / Abbreviations --- p.vii. / Abstract --- p.viii. / Abstract (Chinese) --- p.x. / Chapter Part I --- Synthesis and Characterization of Fluorene-Based Statistical Copolymers / Chapter Chapter I --- Introduction --- p.1 / Chapter 1. --- Background --- p.1 / Chapter 2. --- rinciple of Electroluminescence --- p.2 / Chapter 3. --- Electroluminescence from conjugatedolymers --- p.4 / Chapter 4. --- Device configurations --- p.6 / Chapter 4.1 --- Electrodes selection --- p.8 / Chapter 4.2 --- Charge injection and transporting layers --- p.9 / Chapter 5. --- Device characterizations --- p.12 / Chapter 6. --- Blue-light emittingolymers --- p.14 / Chapter 6.1 --- Fluorene homopolymers --- p.16 / Chapter 6.2 --- Fluorene copolymers --- p.19 / Chapter 6.3 --- Aggregation studies ofolyfluorenes --- p.22 / Chapter 7. --- Synthetic measures toward conjugatedolymers --- p.28 / Chapter Chapter II --- Results and discussion --- p.30 / Chapter 1. --- Synthesis --- p.30 / Chapter 1.1 --- olyfluorene synthesis --- p.30 / Chapter 1.2 --- Fluorene-based statistical copolymers --- p.34 / Chapter 1.2.1 --- Fluorene-biphenyl copolymers --- p.34 / Chapter 1.2.2 --- Fluorene-［2.2]paracyclophane copolymers --- p.37 / Chapter 2. --- Structural characterizations --- p.40 / Chapter 2.1 --- NMR spectroscopic data analyses --- p.40 / Chapter 2.2 --- Gelermeation chromatographic analyses --- p.44 / Chapter 2.3 --- Thermal analyses --- p.47 / Chapter 3. --- Opticalroperties characterizations --- p.50 / Chapter 3.1 --- UV-visible absorptions --- p.50 / Chapter 3.2 --- hotoluminescences --- p.53 / Chapter 3.2.1 --- hotoluminescences in solutions --- p.53 / Chapter 3.2.2 --- hotoluminescences in solid thin films --- p.59 / Chapter 4. --- Device fabrications --- p.61 / Chapter 5. --- I-V characterizations --- p.64 / Chapter 6. --- Electroluminescences --- p.66 / Chapter Chapter III --- Conclusion --- p.68 / Chapter Chapter IV --- Experimental --- p.70 / Reference --- p.77 / Appendix NMR spectra --- p.82 / Chapter Part II --- Regio-Specific Synthesis of Functionalized [2.2]PARACYCLOPHANES / Chapter Chapter I --- Introduction --- p.102 / Chapter 1. --- Background --- p.102 / Chapter 2. --- Synthetic Route to [2.2]Paracyclophane --- p.103 / Chapter 2.1 --- Macrocyclization via Wurtz coupling --- p.103 / Chapter 2.2 --- Extrusion of small gaseous molecules form macrocyclicrecursors --- p.106 / Chapter 2.3 --- Dimerization of/p-xylylene --- p.108 / Chapter 2.4 --- Miscellaneous methods --- p.110 / Chapter 3. --- Synthetic Routes to Substituted [2.2]Paracyclophanes --- p.111 / Chapter 3.1. --- Functionalization of [2.2]pracyclophane --- p.114 / Chapter 3.1.1 --- reparation of mono-substituted [2.2]paracyclophanes --- p.114 / Chapter 3.1.2 --- reparation of di-substituted [2.2]paracyclophanes --- p.117 / Chapter 3.1.3 --- reparation of tri-substituted [2.2]paracyclophanes --- p.120 / Chapter 3.1.4 --- reparation of tetra-substituted [2.2]paracyclophanes --- p.120 / Chapter 3.1.5 --- Functional group conversions in [2.2]paracyclophanes --- p.121 / Chapter Chapter II --- Syntheticlans --- p.124 / Chapter Chapter III --- Results and Discussion --- p.129 / Chapter 1. --- Effect ofolymerization inhibitor --- p.130 / Chapter 2. --- "Synthesis of 4,12-disbstituted [2.2]paracyclophanes" --- p.132 / Chapter 2.1 --- "Synthesis of 4,12-dibromo[2.2]paracyclophane" --- p.132 / Chapter 2.2 --- "Synthesis of 4,12-dichloro[2.2]paracyclophane" --- p.134 / Chapter 2.3 --- "Synthesis of 4,12-dimethyl[2.2]paracyclophane" --- p.135 / Chapter 3. --- "Synthesis of 4,7,13,16-tetrasubstituted [2.2]paracyclophanes" --- p.137 / Chapter 3.1 --- "Synthesis of 4,7,13,16-tetrabromo[2.2]paracyclophane" --- p.137 / Chapter 3.2 --- "Synthesis of 4,7,13,16-tetrabromo[2.2]paracyclophane" --- p.138 / Chapter 4. --- "Synthesis of 4,8,12,16-tetrasubstituted [2.2]paracyclophane" --- p.139 / Chapter 4.1 --- "Synthesis of 4,8,12,16-tetrabromo[2.2]paracyclophane" --- p.139 / Chapter 5. --- Summary --- p.141 / Chapter Chapter IV --- Conclusion --- p.145 / Chapter Chapter V --- Experimental --- p.146 / References --- p.160 / Appendix I X-ray crystallographic data --- p.162 / Appendix II NMR spectra --- p.183

by Mabel Siu-Man Yuen. / Thesis (Ph.D.)--Chinese University of Hong Kong, 1997. / Includes bibliographical references (p. 146-161). / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Mode of access: World Wide Web.

archives@tulane.edu / Abstract Condensation of 1,8,13-tris(mercaptomethyl)triptycene and tris(bromomethyl)methane yields the in,in-cyclophane 30 in 8% yield with two inwardly directed methine groups. The X-ray analysis clearly shows that it is the in,in-isomer. The proton NMR spectrum displays an obvious coupling between the two methine hydrogens, which was proved by selectively irradiation one of the apical methine proton. The coupling constant is 2.0 Hz, which is the largest through-space coupling observed so far. Based on DFT and MP2 calculations, the hydrogen-hydrogen non-bonded contact distance is estimated to be 1.50-1.53 Å. Two in,in-cyclophanes 31 and 56, containing one or two methyl groups in their central cavities, have been synthesized, crystallized and fully characterized by ¹H and ¹³C NMR spectroscopy, MALDI-TOF mass spectrometry, IR spectroscopy, and X-ray crystallography. Cyclophane 31 is the first example of an in,in-cyclophane with a methyl group inside the cavity. The IR spectrum clearly shows that the Si-H stretch is blue-shifted from 2177 cm-1 in an acyclic model to 2269 cm-1. Based on computational studies, cyclophane 31 has a very short non-bonded H---CH3 distance of about 2.30 Å. Cyclophane 56 does not have short non-bonded contact distance, but it is the first example of a macrobicyclic compound that contains two inwardly directed methyl groups. Three cyclophanes with the formula (C28H31PS3)n, where n = 1 or 2, were isolated from the base-promoted macrocyclization of tris(2-mercaptophenyl)phosphine and tris(3-bromopropyl)methane. Spectroscopic and X-ray analysis showed them to be the in,in-isomer 32, the in,out-isomer 60, and a dimeric in,out,in,out-isomer 61. Compounds 32 and 61 display approximately C3-symmetric and Ci-symmetric structures, respectively, in the crystal, but compound 60 adopts two distinct low-symmetry conformations in the solid state. In each case, the observed structures correspond to the lowest energy conformations of their respective isomers as calculated at the B3PW91/6-31G(d) level of theory. The in,in-isomer 32 displays a close contact between the phosphine in-lone pair and the in-methine group, with through-space spin-spin coupling constants of JPH = 9 Hz and JPC = 24 Hz, the latter of which appears to be the largest reported phosphorus-carbon through-space coupling constant. Dodecaphenyltetracene (75), the largest perphenylacene yet prepared, was synthesized from known tetraphenylfuran, hexaphenylisobenzofuran, and 1,2,4,5-tetrabromo-3,6-diphenylbenzene in three steps. The X-ray structure of the deep red, highly luminescent 75 shows it to be a D2-symmetric molecule with an end-to-end twist of 97o. The central acene is encapsulated by the peripheral phenyl substituents, and as a result, the molecule is relatively unreactive and even displays reversible electrochemical oxidation and reduction. Decaphenylphenanthrene (77), the first nonlinear perphenyl polycyclic aromatic hydrocarbon to be prepared so far, has been made from tetraphenylfuran and 1,2,3,4-tetrabromo-5,6-diphenylbenzene in two steps. The X-ray structure contains two independent molecules of 77, and each of them ppssesses approximate C2 symmetry in the crystal. / 1 / yonglong xiao

The syntheses and properties of various cyclophanes have been extensively investigated by Cram and others. The paracyclophanes are compounds in which benzene rings are linked to each other by two saturated chains at the para positions, as in structure I. When they are joined to the meta positions, they are called metacyclophanes.

The photohydrodebromination of brominated paracyclophanes was studied to help elucidate the possible mechanistic pathways leading to product for bromoarenes in general. Several brominated [2.2]paracyclophanes were studied to determine the effect of substitution patterns on this reaction. [2.2]Paracyclophanes were chosen for this study in order to investigate possible intramolecular excimer formation as a route to product formation. The [2.2]paracyclophanes studied were 4-bromo-, pseudo-para-dibromo-, and pseudo-ortho-dibromo[2.2]paracyclophane. 5-Bromo[3.3]paracyclophane has also been studied to determine the effect of increased ring separation on the reaction. These brominated cyclophanes showed varying efficiencies of both intermolecular and intramolecular excimer formation. / Graduation date: 1993

Thesis (Ph.D.), Memorial University of Newfoundland, 2000. / Includes bibliographical references.

by Fong Sun. / On t.p., "+" appears over "-". / Thesis (M.Phil.)--Chinese University of Hong Kong, 1994. / Includes bibliographical references (leaves 41-43). / Acknowledgements --- p.i / Contents --- p.ii / Abstract --- p.iii / Abbreviations --- p.iv / Chapter I --- Introduction / Chapter I-1 --- General background --- p.1 / Chapter I-2 --- Literature survey --- p.3 / Chapter I-2-1 --- Ley's approach to β-ketomacrolides --- p.3 / Chapter I-2-2 --- Weiler's approach to β-ketomacrolides --- p.4 / Chapter I-2-3 --- Macrocyclic β-ketomacrolides formation through sulfide contraction ´ؤIreland's approach --- p.5 / Chapter II --- Result and Discussion / Chapter II-1 --- General strategy for the synthesis of 1 -oxa[n]metacyclophanes --- p.7 / Chapter II-2 --- l-Oxa[n]metacyclophanes as masked β-ketomacrolides synthons --- p.9 / Chapter II-3 --- Application to the synthesis of natural products --- p.10 / Chapter II-4 --- An alternate approach for the synthesis of (2E)-2-dodecen-l 1-olide´ؤA structural proof --- p.15 / Chapter III --- Conclusion --- p.17 / Chapter IV --- Experimental --- p.18 / Chapter V --- References --- p.41 / Chapter VI --- Spectra --- p.44

Graduate

In the context of new π-donor molecules, extended tetrathiafulvalenes have been widely studies for their use as components of electronically conductive charge-transfer materials. In contrast with the planar π -systems, we have focused our attention on extended tetrathiafulvalenes containing a conjugated anthracenyl spacer (anthracenediylidene derivatives). These TTF derivatives adopt a saddle-shaped conformation in the neutral state and a drastic change of conformation occurs upon oxidation to the dication species. Our main objective was to investigate the molecular and supramolecular architecture of these compounds. At the molecular scale, we synthesised cyclophanes by bridging the preformed anthracene tetrathiafulvalene system and studied their redox properties and crystal packing. We developed the chemistry of anthracenediylidene derivatives in order to direct the supramolecular architecture by secondary interactions (hydrogen-bonding, π-π stacking). Finally, we also investigated the incorporation of anthracenediylidene units inside dendritic structures in order to study the highly charged species formed upon oxidation.