Cheng, Yat Ho. / Thesis submitted in: October 2007. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2008. / Includes bibliographical references. / Abstracts in English and Chinese. / Abstract --- p.i / 摘要 --- p.iii / Acknowledgment --- p.iv / Contents --- p.v / Abbreviations --- p.xi / Chapter Chapter I. --- Model Studies for Catechol Dioxygenases / Chapter I.1 --- General Background / Chapter I.2 --- Intradiol-Cleaving Catechol Dioxygenases --- p.2-4 / Chapter I.3 --- Extradiol-Cleaving Catechol Dioxygenases --- p.5-8 / Chapter I.4 --- Selectivity of Intra- versus Extradiol-Cleaving Pathways --- p.8-10 / Chapter I.5 --- Early Studies on Model Complexes for Catechol Dioxygenases --- p.10-16 / Chapter I.6 --- Spin Crossover Study of Model Complexes --- p.16-18 / Chapter I.7 --- Model complexes for the Extradiol-Cleaving Dioxygenases --- p.19-23 / Chapter I.8 --- Objectives of this Work --- p.23 / Chapter I.9 --- References for Chapter I --- p.24-31 / Chapter Chapter II. --- "Synthesis and Reactivity Studies of Model Complexes of Catechol Dioxygenases Supported by the anionic Hydrotris-3,5-dimethylpyrazolylborate Ligand" / Chapter II.1 --- Introduction --- p.32-33 / Chapter II.2 --- Result and Discussion --- p.34-60 / Chapter II.2.1 --- Synthesis of Iron(III) Catecholate Complexes --- p.34-37 / Chapter II.2.2 --- Molecular Structures --- p.38-45 / Chapter II.2.3 --- Electrochemical Studies --- p.46-48 / Chapter II.2.4 --- UV-Vis Spectroscopic Studies --- p.49-55 / Chapter II.2.4.1 --- Oxygenation Studies of the Catecholate Complexes --- p.49-51 / Chapter II.2.4.2 --- Spectral Studies at low Temperature --- p.52-54 / Chapter II.2.4.3 --- Reactivity Studies with Excess Pyrazole --- p.54-55 / Chapter II.2.5 --- Identification of the degradation products --- p.56-60 / Chapter II.3 --- Summary --- p.61 / Chapter II.4 --- Experiments for Chapter II --- p.62-66 / Chapter II.4.1 --- Materials --- p.62 / Chapter II.4.2 --- Synthesis of complexes --- p.62-64 / Chapter II.4.3 --- Characterization of degradation products --- p.65-66 / Chapter II.5 --- References for Chapter II --- p.67-70 / Chapter Chapter III. --- "Synthesis and Reactivity Studies of Model Complexes of Catechol Dioxygenases Supported by the neutral Hydrotris-3,5-dimethylpyrazolylmethane Ligand" / Chapter III.1 --- Introduction --- p.71-72 / Chapter III.2 --- Results and Discussion --- p.73-96 / Chapter III.2.1 --- Synthesis --- p.73-78 / Chapter III.2.1.1 --- Synthesis of Iron(III)-Catecholate Complexes --- p.73-74 / Chapter III.2.2.2 --- Attempt to Synthesis Iron(III)-Catecholate Complexes with Pyrocatechol --- p.75-76 / Chapter III.2.2.3 --- Attempts to Remove the Chloride Ligand from the Iron(III) Catecholate Complexes --- p.76-77 / Chapter III.2.2.4 --- Synthesis of Iron(II)-Catecholate Complexes --- p.77-78 / Chapter III.2.2 --- Molecular Structures --- p.79-85 / Chapter III.2.3 --- Electrochemical Studies --- p.86-88 / Chapter III.2.4 --- UV-Vis Spectroscopic and Reactivity Studies on Oxygenation of / Chapter III.2.4.1 --- Oxygenation Studies of the Catecholate Complexes --- p.89-90 / Chapter III.2.4.2 --- Spectral changes with chloride removed from the catecholate complex --- p.91-93 / Chapter III.2.5 --- Identification of the degradation products --- p.94-96 / Chapter III.3 --- Summary --- p.96 / Chapter III.4 --- Experimental for Chapter III --- p.97-101 / Chapter III.4.1 --- Materials --- p.97 / Chapter III.4.2 --- Synthesis of complexes --- p.97-99 / Chapter III.4.3 --- Characterization of Oxygenation Products --- p.100 / Chapter III.5 --- References for Chapter III --- p.101-105 / Chapter Chapter IV. --- "Synthesis and Reactivity Studies of Manganese and Cobalt Catecholate Complexes Supported by the anionic Hydrotris-3,5-dimethyl -pyrazolylborate Ligand" / Chapter IV.1 --- Introduction --- p.106-109 / Chapter IV.2 --- Results and Discussion --- p.110-127 / Chapter IV.2.1 --- Synthesis of Manganese and Cobalt Catecholate Complexes --- p.110-111 / Chapter IV.2.2 --- Molecular Structures --- p.112-118 / Chapter IV.2.3 --- UV-Vis Spectroscopic Studies and Reactivity Studies --- p.119-124 / Chapter IV.2.3.1 --- Oxygenation studies of the Manganese(III)-Catecholate Complex --- p.119-121 / Chapter IV.2.3.1 --- Oxygenation studies of the Cobalt(II)-catecholate Comple --- p.x / Chapter IV.2.4 --- Identification of Degradation Products --- p.124-126 / Chapter IV.3 --- Summary --- p.126 / Chapter IV.4 --- Experimental for Chapter IV --- p.127-129 / Chapter IV.4.1 --- Materials --- p.127 / Chapter IV.4.2 --- Synthesis of complexes --- p.127-129 / Chapter IV.5 --- References for Chapter IV --- p.130-135 / Appendix I / Chapter A.I.1 --- General Procedure --- p.136 / Chapter A.I.2 --- Physical Characterization --- p.136-138 / Appendix II / Chapter A.II.1 --- "Selected Crystallographic Data for Compounds 1，2，4,5，7，9，14，15，16，17 and 18" --- p.142-147 / Chapter A.II.2 --- 1H and 13C NMR Spectra --- p.148-150 / Chapter A.II.3 --- Chromatogram and Mass spectra (El and Cl) from GCMS Analysis --- p.151-157 / Chapter A.II.4 --- Mass Spectra --- p.158-162

本文成功地合成了碳碳相連的鳥巢型碳硼烷化合物[Me₃NH][7,8-O(CH₂)₂-7,8-C₂B₉H₁₀]，閉籠型碳硼烷衍生物1-(1-茚基)-1,2-碳硼烷以及一系列基於以上配體的稀土金屬配合物，同時研究並探討了這些化合物對不同不飽和有機化合物的反應性。 / 1-(1-茚基)-1,2-碳硼烷可通過碳硼烷二鋰鹽與相應環氧化合物反應後再脫水而製備。該配體與稀土烷基化合物發生酸碱反應生成相應的稀土碳硼烷化合物，[η⁵:σ-(C₉H₆)C₂B₁₀H₁₀]Ln[σ:σ-(CH₂C₆H₄-o-NMe₂)](THF)₂ (Ln= Y, Gd, Er, Dy)。這類稀土碳硼烷化合物的反應性也被相繼研究。它可以跟各種不飽和底物（如碳二亞胺，異氰，異硫氰酸鹽，異氰酸酯）反應。其中和R-N=C=N-R (R= TMS, tBu) 反应生成相應的單插入產物。这些单插入产物可以继续和小分子反应插入稀土金屬碳硼烷碳鍵得到双插入产物。並且，這類稀土碳硼烷化合物也可以發生質子化反應生成對應的離子型化合物。 / [Me₃NH][7,8-O(CH₂)₂-7,8-C₂B₉H₁₀]可通過(CH₂OCH₂)C₂B₁₀H₁₀的脫硼反應製備，它與Ln(CH₂-o-C₆H₄-NMe₂)₃ (Ln = Y, Gd, Er, Dy)反應得到半夾心金屬碳硼烷 [η⁵-(CH₂OCH₂)C₂B₉H₉]Ln(CH₂-o-C₆H₄-NMe₂)(THF)₂.不飽和的極性有機不飽合底物可以插入金屬碳鍵，并在取代基的空間位阻效應的影響下生成單插入或者雙插入的產物。 / 該論文中也研究了[η⁵:σ-(C₉H₆)C₂B₁₀H₁₀]Ln[σ:σ-(CH₂C₆H₄-o-NMe₂)](THF)₂和[η⁵-(CH₂OCH₂)C₂B₉H₉]Ln[σ:σ-(CH₂C₆H₄-o-NMe₂)](THF)₂與不同的Brønsted酸的酸堿反應。[η⁵-(CH₂OCH₂)C₂B₉H₉]Y[σ:σ-(CH₂C₆H₄-o-NMe₂)](THF)₂ 同各種各樣的胍反應生成相應的胍基化合物。 / 最後，1-(1-茚基)-1,2-碳硼烷發生脫硼反應可生成對應的[Me₃NH][(C₉H₇)C₂B₉H₁₁]。該配體同Y(CH₂-o-C₆H₄-NMe₂)₃反應得到的稀土烷基化合物[(1-C₉H₆)(C₂B₉H₁₀)]Y(DME)₂也進一步的進行了研究。它同二苯酮，二苯基乙烯酮，二（2-吡啶基）甲酮以及其他不飽和有機化合物反應，得到具有類似結構的單插入產物。 / C,C'-Linked dicarbollide species [Me₃NH][7,8-CH₂OCH₂-7,8-C₂B₉H₁₀] and 1-(1-indenyl)-1,2-carborane were synthesized. Their applications in rare earth chemistry were studied and discussed in this thesis. / 1-(1-Indenyl)-1,2-carborane was synthesized from the reaction of indene epoxide with dilithium salt of carborane. Reaction of this ligand with Ln(CH₂C₆H₄-o-NMe₂)₃ (Ln = Y, Gd, Er, Dy) led to the formation of [η⁵:σ-(C₉H₆)C₂B₁₀H₁₀]Ln[σ:σ-(CH₂C₆H₄-o-NMe₂)](THF)₂ (Ln= Y, Gd, Er, Dy). The metal-carbon σ bond in these complexes was reactive toward unsaturated polar organic substrates, such as carbodiimide, isocyanide, isothiocyanate, and isocynate. They reacted with R-N=C=N-R (R= TMS, tBu) to form mono-insertion products. The metal-cage carbon σ bond in the mono-insertion product was also active toward unsaturated polar organic substrates to form di-insertion complexes. And the indenyl-carboranyl gadolinium complex can be protonated to give ionic species. / [Me₃NH][7,8-CH₂OCH₂-7,8-C₂B₉H₁₀] was prepared by the deboration reaction of (CH₂OCH₂)C₂B₁₀H₁₀. Ln(CH₂C₆H₄-o-NMe₂)₃ (Ln = Y, Gd, Er) reacted with this ligand to form half-sandwich metallacarboranes [η⁵ -(CH₂OCH₂)C₂B₉H₉]Ln[σ:σ-(CH₂C₆H₄-o-NMe₂)](THF)₂. Unsaturated polar organic substrates, such as isocyanide, isothiocyanate, and isocynate can insert into the M-C bond to form mono-insertion complexes or di-insertion complexes depending on the steric factor of the substrate. / Acid-base reactions of [η⁵:σ-(C₉H₆)C₂B₁₀H₁₀]Ln[σ:σ-(CH₂C₆H₄-o-NMe₂)](THF)₂ and [σ:η⁵-O(CH₂)₂C₂B₉H₉]Y[σ:σ-(CH₂C₆H₄-o-NMe₂)](THF)₂ were studied. Complex [σ:η⁵-O(CH₂)₂C₂B₉H₉]Y[σ:σ-(CH₂C₆H₄-o-NMe₂)](THF)₂ reacted with various guanidines to give the corresponding guanidinato products. / Complex [(1-C₉H₆)(C₂B₉H₁₀)]Y(DME)₂ was synthesized and structurally characterized from the reaction of [Me₃NH][(C₉H₇)C₂B₉H₁₁] with Y(CH₂-o-NMe₂-C₆H₄)₃ in DME. Its reactivity was examined. It reacted with diphenylketone, diphenylketene, di(2-pyridyl)ketone and other unsaturated organic compounds to afford mono-insertion products with similar structures. / 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. / Yang, Jingying. / Thesis (Ph.D.) Chinese University of Hong Kong, 2014. / Includes bibliographical references (leaves 113-124). / Abstracts also in Chinese.

Organic light emitting diodes (OLEDs) are an emerging display technology with the advantages of being efficient, bright, portable and flexible. In this work, a number of novel compounds have been developed for incorporation into OLEDs as emitting dopants. A series of ligands containing dipyrido[3,2-a:2�,3�-c]phenazine substituted at the 11-position with ethyl ester, bromo-, nitrile and 5-phenyl-1,3,4-oxadiazole moieties have been synthesised. Each of the ligands were coordinated to Re(I), Cu(I), Ru(II) and Ir(III) metal centres. Ligands and complexes were characterised by �H NMR and IR spectroscopy, mass spectrometry and microanalysis. Single crystal X-ray analyses were performed on fac-chlorotricarbonyl(dipyrido[3,2-a:2�,3�-c]phenazine-11-carboxylic ethyl ester)rhenium (triclinic, P-1, a = 6.403(5) Å, b = 10.388(5) Å, c = 16.976(5) Å, α = 84.087(5)�, β = 84.161(5)�, γ = 79.369(5)�, Z = 2, R1 = 0.0536, wR2 = 0.0978), fac-chlorotricarbonyl(11-bromodipyrido[3,2-a:2�,3�-c]phenazine)rhenium.CH₃OH (monoclinic, C2/c, a = 19.506(5) Å, b = 18.043(5) Å, c = 13.320(5) Å, α = γ = 90�, β = 114.936(5)�, Z = 4, R1 = 0.0345, wR2 = 0.0827), fac-chlorotricarbonyl(11-cyanodipyrido[3,2-a:2�,3�-c]phenazine)rhenium (triclinic, P-1, a = 6.509(5) Å, b = 12.403(5) Å, c = 13.907(5) Å, α = 96.88(5)�, β = 92.41(5)�, γ = 92.13(5)�, Z = 2, R1 = 0.0329, wR2 = 0.0701), bis-2,2�-bipyridyl(2-(11-dipyrido[3,2-a:2�,3�-c]phenazine)-5-phenyl-1,3,4-oxadiazole)ruthenium triflate.2CH₃CN (triclinic, P-1, a = 10.601(5) Å, b = 12.420(5) Å, c = 20.066(5) Å, α = 92.846(5)�, β = 96.493(5)�, γ = 103.720(5)�, Z = 2, R1 = 0.0650, wR2 = 0.1458) and bis-(2-phenylpyridine-C�,N�)(dipyrido[3,2-a:2�,3�-c]phenazine)iridium(III) hexafluorophosphate.(CH₃)₂CO (triclinic, P-1, a = 13.505(5) Å, b = 16.193(5) Å, c = 19.788(5) Å, α = 92.857(5)�, β = 98.710(5)�, γ = 93.432(5)�, Z = 2, R1 = 0.0494, wR2 = 0.1097). The ground and excited state properties of the ligands and complexes were investigated by a range of techniques, including electrochemistry, absorption and emission spectroscopy, spectroelectrochemistry and excited state lifetime studies. Complexes of dppz-based ligands typically show MOs which are segregated over either the bpy or phz region of the dppz backbone. The properties of the Ru(II) and Ir(III) complexes of the ligand series investigated in this work were consistent with this model, and the LUMOs of these complexes were assigned as the b₁(phz) phz-localised MO. The Re(I) and Cu(I) complexes of the ligand series appeared to show MOs which were delocalised over the entire dppz ligand. A modular complex containing an electron transport group, hole transport group and emitting centre was synthesised. The complex fac-tricarbonyl(trans-(E)-1-((2,2�:5�,2��-terthiophen)-3�-yl)-2-(4�-pyridyl)-ethane)(2-(11-dipyrido[3,2-a:2�,3�-c]phenazine)-5-phenyl-1,3,4-oxadiazole)rhenium(I) hexafluorophosphate was oxidised and reduced readily, encouraging efficient transport of both holes and electrons. However, this resulted in the complex having a small band gap and hence a low quantum yield of emission. Emission from this complex appeared to be from more than one state. The complexes containing the dppz-based ligand series show complicated excited state behaviour. Emission behaviour is consistent with input from more than one state for many of the Re(I), Cu(I) and Ir(III) complexes. The Ru(II) complexes of the ligand series emit from a �MLCT state between metal-based and bpy-based MOs located on the dppz ligands, as is usual for complexes of this type. All complexes containing 11-cyanodipyrido[3,2-a:2�,3�-c]phenazine showed extremely short excited state lifetimes consistent with extremely efficient non-radiative deactivation of the excited state. Ligands and complexes were incorporated into OLEDs with the structure [ITO/PEDOT:PSS/PVK:BuPBD:dopant/BCP/Alq₃/LiF/Al] to test their ability to behave as emissive dyes. Many of the compounds behaved poorly as dopants due to their low emission quantum yields, and poor alignment of HOMO and LUMO energy levels with those of the other compounds within the device. �MLCT-based emission was achieved through energy transfer from the PVK host for the devices containing chlorotricarbonylrhenium(I) complexes of the ligand series. The OLEDs containing Ru(II) and Ir(III) complexes also emitted from dopant-centred �MLCT states. In these devices, dopant excitation appeared to occur through direct charge trapping from the adjacent hole transport and electron transport layers.

Thesis (Ph.D.)--Baylor University, 2005. / Includes bibliographical references (p. 273-283).

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

No description available.

­^¤åºK­n Chapter 1 A new chelating N,N ligand family incorporating an anilido-phosphinimine donor set has been designed. The ligand1-(NHAr)-2-(PPh2=NAr¡¦)C6H4(iPr[NN]DippH: Ar = 2,6-iPr2-C6H3, Ar¡¦ = 2,6-iPr2-C6H3; iPr [NN]MesH: Ar = 2,6-iPr2-C6H3, Ar¡¦ = 2, 4, 6-Me3C6H2; Me[NN]MesH: 2,6-Me2-C6H3, Ar¡¦ = 2, 4, 6-Me3C6H2) were synthesized via a route of reacting amido phosphine ligands with aryl azides. We observed different behaviors of adding n-BuLi in different solvents. In 31P NMR, we found the changed of chemical shift upon the different Ar¡¦ substituents. When substituent on Nphosphinimine was Dipp, there are larger chemical shift change. Addition of [NN]H to ZnMe2 or ZnEt2 in toluene or Et2O at -35oC generated the monomeric, three-coodinate [NN]ZnR (R = Me, Et)(schem 1), while the metathesis reaction of Zn(OAc)2 with iPr[NN]DippLi(Et2O) in THF at -35oC produced iPr[NN]DippZnOAc. But in the same condition, we made the iPr[NP] iPrLi(DME) produced homoleptic {iPr[NP] iPr}2Zn. All of the complexes were characterized by multinuclear NMR spectroscopy or X-ray crystallography. We used [NN]ZnR catalyzed ring-opening polymerization of £`-Caprolactone . The results of catalysis had good yields in 90 to 100% and narrow PDI around 1.5. But they are not a living polymerization catalysis. Chapter 2 We use {[NP]NiCl}2 catalyzed Kumada reactions of alkyl halide or aryl halide with Grignard reagent. In the result, Used {iPr[NP]iPr}2NiCl catalyzed aryl halide with Grignard reagent is better than other {[NP]}2NiCl, but not good catalyzed alkyl halide with Grignard reagent. We do kinetic studies of benzene C-H bond activation by nickel complexes of amido phosphine ligand. By the result, We can defind the benzene C-H bond activation was association rection.

Thesis (Ph. D.)--University of Akron, Dept. of Chemistry, 2009. / "May, 2009." Title from electronic dissertation title page (viewed 11/25/2009). Advisor, Michael J. Taschner; Committee members, David Modarelli, Jun Hu, Wiley J. Youngs, Amy Milsted; Department Chair, Kim C. Calvo; Dean of the College, Chand Midha; Dean of the Graduate School, George R. Newkome. Includes bibliographical references.

Reproduction de : Thèse doctorat : Pharmacie. Biologie moléculaire et physiologie : Reims : 2005. / Bibliogr. p.180-217. Index.

Thèse de doctorat : Chimie : Strasbourg 1 : 2008. Thèse de doctorat : Chimie : Université de Barcelone : 2008. / Thèse soutenue en co-tutelle. Titre provenant de l'écran-titre. Notes bibliogr.