This thesis describes three types of reactions that were carried out using iridium catalysts. The first type is the iridium-catalyzed asymmetric hydrogenation of olefins. In paper I, the preparation of a new type of bicyclic thiazole-phosphine based iridium complex was described. The new catalysts have displayed high activity and enantioselectivity in the asymmetric hydrogenation of unfunctionalized olefins. Papers II and III focus on the expansion of the substrate scope for the iridium catalyzed asymmetric hydrogenation in which a number of heterocyclic olefins were evaluated. In paper IV, the enantioselective asymmetric hydrogenation of α, β-unsaturated esters was described. The chiral products bearing tertiary stereogenic centers obtained by hydrogenation have great synthetic value and have been used in the synthesis of pharmaceuticals as well as in the total synthesis of natural products. The second type is the asymmetric isomerization of allylic alcohols. In paper V, both cis and trans primary allylic alcohols were isomerized to the corresponding β-chiral aldehydes in high enantioselectivities by an N,P-chelating iridium complex. The third type is the selective mono-N-alkylation of amines with alcohols. In paper VI, a phosphine/NHC based iridium catalyst was synthesized and applied in the alkylation of amines. It is the first time that this type of transformation is carried out at room temperature.

Thesis (Ph.D.)--Hong Kong University of Science and Technology, 2005. / Includes bibliographical references. Also available in electronic version.

>Magister Scientiae - MSc / A novel 3-mercaptopropionic acid capped iridium selenide quantum dots based label free impedimetric immunosensor was successfully constructed. The 3-mercaptopropionic acid capped iridium selenide quantum dots synthesized were studied using HRTEM, revealing the formation of very small sizes, of about 3 nm. The optical Uv-Vis absorption wavelength of the quantum dots is blue-shifted, a phenomenon explained by the effective mass approximation (EMA) for semiconducting materials with sizes below 10 nm. Using cyclic voltammetry it is noted that the quantum dots have interesting electro-catalytical properties. The immunosensor proved to be sensitive towards nodularin, with a very low detection limit of 0.009 ng/mL and is significantly lower than the recent anti-nodularin ELISA kit developed by (Zhou et al., 2011) which has a detection limit of 0.16 ng/mL.Also the dection limit of the immunosensor is below the South African guideline value for microcystin-LR (0-0.8) μg/L (DWAF; 1996). The calibration curve of the 3MPA-GaSe nanocrystal based biosensor was successfully constructed, which exhibited a trend described by Michaelis-Menten, a typical behaviour of enzymatic biosensors. The detection limit of the biosensor is 0.004 nM and is significantly lower than the action limit of 17beta-estradiol, (1.47 x 10-10 M).

The x-ray structures of several alkyl halide, alkyl dihalide, and hydrogen adducts to pyrazolyl-bridged diiridium complexes [special characters omitted] are determined. The diiridium (bis-pyrazolyl) core of these complexes enables contact between the two centers so that metal-metal bond formation may occur, exemplified by a short iridium-iridium distance of 2.78(I) A in the diiridium(II) complex [special characters omitted]. Oxidation mechanisms are postulated based on reaction kinetics. The oxidative addition of methyl iodide to [special characters omitted] is observed to occur by a two-step mechanism, where a high positive ΔS‡ term may be due to a highly ordered intermediate. This is proposed as evidence for an [special characters omitted] addition, where coordination of the alkyl halide is followed by halide dissociation and migration to a trans diaxial coordination site. Different kinetics of the reaction are observed in THF and benzene, which is also attributed to a polar [special characters omitted] intermediate. Occupation of the 3,3’ and 5,5’ positions of the pyrazolyl ligand decreases the reaction rate by an order of magnitude or greater, which indicates steric inhibition of the reaction by the bridging ligands. Experimental evidence for a competing light-induced reaction that corresponds to a radical-chain mechanism rather than the dark [special characters omitted] reaction is also presented. Oxidative isomerization of an iodo (iodomethylene) complex to the methylene-bridged isomer is determined to be an intramolecular process based on isotope labelling experiments and kinetics. Negligible isomerization to the bridging methylene complex under ambient conditions is attributed to coordinative saturation; the stability of [special characters omitted] is likewise due to coordinative saturation of the metal centers. The addition of hydrogen or hydride to [special characters omitted] is possible through a number of synthetic routes, but the stereochemistry of the iridium(II) hydrido complexes is such that the metal-hydride and iridium-iridium bonds do not occupy coordination sites trans to each other: it is proposed that the strong σ-trans effect of the hydride induces structural rearrangements in substitution reactions so that stereochemistry of parent complexes is not conserved. This is demonstrated by the x-ray structures of [special characters omitted]. The hydride ligand promotes nucleophilic attack on an electron-rich iridium center; thus water and other Lewis bases are found to react with the cationic diiridium hydride complex [special characters omitted]. / Graduate

This thesis considers the electrochemistry of platinum-iridium electrodes in both sulphate- and chloride-containing electrolytes at 20 - 25°C. Both wire electrodes of appropriate alloy compositions and titanium-substrate electrodes were employed. Polarization curves were obtained, and a technique for measuring the surface area of the electrodes was employed in order to determine the effect of potentiostatic electrolysis on the electrochemically active area. The wire alloy electrodes showed polarization behaviour in 1M NaCl; pH 2 identical to that of platinum electrodes, indicating that iridium is not effective in reducing the passivation of these electrodes even with up to 25% alloy content. The coated electrodes showed irreversible surface area losses in both sulphate and chloride electrolytes, with the latter producing significant reductions after very short polarization times. It is suggested that oxidation of the substrate leading to electrical isolation of coating plates is responsible for the area decay. / Science, Faculty of / Earth, Ocean and Atmospheric Sciences, Department of / Graduate

No description available.

Dramatic increase of energy consumption and environmental problems invigorate the development of organic semi-conductive materials to substitute for the conventional inorganic materials in the application of photovoltaic and light-emitting devices. In view of the merits of low driving voltage, high power conversion efficiency, large-area fabrication of thin and light organic films as well as saturated emission, organic light-emitting diodes (OLEDs) have received much more consideration by scientists in the past two decades. And even out of laboratory, the OLEDs are popular among the commercial electronic products for solid-state displays and illumination. Generally, three primary RGB emitters, involving red (R), green (G) and blue (B), are footstones to achieve solid-state displays and illumination because the spectra by compositing RGB emissions match very well with the solar spectrum. Also, the combination of two complementary luminophors, blue and orange or yellow is an alternative approach to simulate the solar spectrum for white light illumination. Except for the full-color light-emitting materials for solid-state displays and illumination, near infrared (NIR) organics are of great importance for applications in information-secured devices, communications, biosensors, and phototherapy. To date, uncountable research works focusing on the emitters for full-color emissions have demonstrated their synthesis, photophysical properties and OLED application, which shows enough efficiency and stability to commercial utility. However, there are still three challenging issues which are needed to be handled urgently. Firstly, the lack of efficient deep blue emitters makes the external quantum efficiency (EQE) of deep blue OLEDs around 10% when the Commission Internationale de l'Éclairage (CIE) coordinates of y is smaller than 0.1. On the one hand it is difficult to achieve the deep blue emitters with extremely broad energy gap between the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO). On the other hand the triplet and frontier energy levels of the host, electron transporting layer (ETL) and hole transporting layer (HTL) in the device are required to well match with that of the emitters. Secondly, high energy in the emissive layer (EML) of deep blue OLEDs may degrade the materials used inside the EML, resulting in their short lifetimes. Thirdly, by comparison with other colors, the investigations of NIR emitters, such as their preparation, property study and device fabrications are sparse.;By harvesting both 25% singlet and 75% triplet excited states, iridium(III) [Ir(III)] complexes have been proven to be one of the best candidates to achieve highly efficient phosphorescent OLEDs (PHOLEDs) for solid-state displays and illumination. Herein, based on Ir(III) complexes, 18 phosphors were synthesized to achieve a widely tunable phosphorescence from deep blue to NIR. In this thesis, their synthesis were fully characterized by NMR spectroscopy, mass spectrometry and X-ray crystallography. Further investigations on the photophysical, electrochemical and thermal properties reveal that these phosphors have the possibility of device fabrication. And rational design of device architectures afford the OLEDs with high efficiencies.;Firstly, N-heterocyclic carbene ligands (CˆC:) were used to elevate the LUMO of phosphors (Ir1-Ir7), resulting in true and deep blue emission spanning from 420 to 450 nm. Secondly, the widely tunable phosphorescence from 470 to 614 nm was accomplished by using polyfluorinated 2-phenylpyridine (CˆN) derivatives as cyclometallated ligands of Ir(III) complexes (Ir10-Ir17). Interestingly, electron-withdrawing trifluoromethyl (CF3) group on the phenyl ring of CˆN-type ligands results in significantly red-shifted emissions of Ir(III) complexes, which distinguishes with the blue-shift effect of fluoride approach. Lastly, by comparison with the reported literature on NIR Ir(III) phosphors with extensive conjugation, the addition of slight conjugation but electron-withdrawing moieties onto the pyridyl ligands is a powerful and convenient avenue to tune the phosphorescence of Ir(III) phosphor into the NIR region, emitting at 729 nm.;Meanwhile, the deepest blue OLED made from Ir1 showed a peak EQE of 7.1% with CIE of (0.16, 0.11). And the best deep blue OLEDs made from Ir7 by using single and double electroluminescent (EL) units gave the highest EQE of 19.0% and 31.5% with CIE coordinates of (0.15, 0.19) and (0.15, 0.22), respectively. Such high efficiencies are comparable to and even better than the currently reported deep blue PHOLEDs. Also, the sky blue, green, yellow, orange, red and NIR PHOLEDs fabricated from Ir10, Ir13, Ir15, Ir16, Ir17 and Ir18 afforded the maximum EQE of 11.2%, 20.1%, 15.4%, 9.9%, 6.8% and 4.0%, respectively. By stacking RGB EML, the white PHOLED (PHWOLED) made by Ir1, Ir13 and Ir17 gave a peak EQE of 16.0% and CIE of (0.36, 0.47).;All in all, this thesis has successfully combined the materials synthesis and devices design to achieve efficient full-color and NIR PHOLEDs which are of great interest for solid-state displays and illumination. These works have a great significance in terms of the improvement of efficiency and stability of deep blue OLEDs as well as simplifying the synthesis methods to prepare highly efficient NIR Ir(III) phosphors.

No description available.

Thermal reactions of the iridium complex, [Ir(COD)(PMe₃)₃]Cl (COD=1, 5 Cyclooctadiene), with benzene, benzaldehyde, pyridine, and furan yield the C-H addition products of mer-(Me₃P)₃Ir(Phenyl)(H)C! (1), mer-(Me₃P)₃Ir(COC₆H₅)(H)Cl (II), mer-(Me₃P)₃Ir(Pyridyl)(H)Cl (IID, and mer-(Me₃P)₃Ir(furyl)Cl (IV), respectively. Each of these complexes was characterized by 1H, 13C, 31P NMR spectroscopy and single crystal X-ray diffraction. Thermal reaction of the [Ir(COD)(PMe₃)₃]CI with thiophene and benzothiophene produced the C-S addition products forming thiometallacycles of (Me₃P)₃Ir-(CH=CHCH=CHS)CI(V), and (Me₃P)₃Ir(CH=CH-C₆H₄S)Cl (VI). The C-H addition products are unreactive and require the aid of TI[PF6] to remove the chloride ligand to provide an open coordination site. Complex (I) and 3,3-dimethyl-1-butyne, produced a 1,4-di-t-butyldienyl complex (VIII) by a double insertion of the alkyne with one t-butyl group forming an agostic interaction with iridium. Deuterium labeling experiments revealed the mechanism to involve: initial acetylene coordination after the chloride ligand was removed by TI⁺ followed by a hydride migration forming a vinyl complex and allowing a second alkyne to coordinate, rearrangement of the second alkyne into a vinylidene and finally a migratory-insertion of the vinyl group unto the vinylidene to form (VIII). Complex (III) and two equivalence of 3,3-dimethyl-1-butyne produced a trans diacetylide complex (XII). The pyridyl ligand was able to remove acidic protons via the nitrogen lone pair, thus altering the course of the reaction. Initial investigations have led to a possible mechanism. Complex (IV) and 3,3-dimethyl-1-butyne gave an interesting hydrido metallo-vinyl complex (XIV) with the t-butyl group forming an agostic CH-Ir interaction. A deuterium labeling experiment revealed the alkyne to initially coordinate and rearrange into a vinylidene, followed by migratory-insertion of the furan group unto the vinylidene to give (XIV). The furyl group is believed to stabilize the initial intermediate by forming a five coordinate square pyramidal complex through the donation of a pair of electrons from the oxygen atom. Reductive elimination of (XIV) using elevated temperatures gave exclusively the trans 3,3-dimethyl-1-(2 furanyl) -1-butyne (XV). The resonance structure found in (IV) is the most important feature of this work. While most insertions occur between the M-H bond, the resonance structure found in (IV) provides the necessary means for insertion of unsaturates to occur between the M-C bond, leaving the M-H bond intact. In conclusion, it appears that the reactivity of the phenyl complex (I) is dependent on the alkyne used. While the reactivity of the pyridyl complex (III) is governed by the nitrogen lone pair; the reactivity of the furanyl complex (IV) follows a different pathway due to resonance stability of the furanyl ligand. / Ph. D.

Depuis quelques années, la recherche et le développement dans le domaine des matériaux électroluminescents suscite de plus en plus d’intérêt. La crise énergétique que nous connaissons actuellement motive un changement de mentalité de la société, de plus en plus soucieuse d’économiser l’énergie. Peu à peu, la commercialisation de diodes électroluminescentes telles que les LEDs (Light-Emitting Diodes) ou les OLEDs (Organic Light-Emitting Diodes) s’est implantée et elle connait aujourd’hui un essor considérable. Néanmoins, de nombreuses améliorations doivent encore être apportées afin d’en optimiser les propriétés. C’est dans cette thématique des matériaux électroluminescents que s’est focalisé notre travail. La préparation de nouveaux composés et l’étude de leurs propriétés photophysiques représentent en effet des étapes déterminantes et indispensables à la fabrication de ces dispositifs. <p><p>Notre travail s’est concentré plus particulièrement sur des complexes de Rh(III), Ir(III) et Ru(II) incorporant un ou plusieurs dérivés du dipyrrométhène. Le premier volet de cette thèse est consacré à la synthèse de quatre complexes mononucléaires [Rh(dipy)3], [Rh(ppy)2dipy], [Ir(ppy)2dipy], [Ru(phen)2dipy]+ dont nous avons ensuite étudié les propriétés photophysiques et électrochimiques. Des calculs théoriques TD-DFT ont également permis de conforter l’attribution de la nature des différents états excités responsables de la luminescence de ces composés. <p>Le second volet de cette thèse est consacré à la mise au point de complexes dinucléaires à l’aide d’un dérivé pontant du dipyrrométhène, avec lequel deux composés ont été obtenus :[Ir2(ppy)4µdipy] et [Rh2(ppy)4µdipy]. Une étude complète du composé d’iridium nous a permis de déterminer ses propriétés. Les nombreux problèmes de solubilité que nous avons rencontrés avec le composé de rhodium ne nous ont pas permis de mener des études approfondies de ce composé.<p>Lors d’un essai de synthèse du composé dinucléaire d’iridium, nous avons isolé le complexe mononucléaire pontant [Ir(ppy)2µdipyH]. Afin de l’engager dans la préparation d’un complexe hétérodinucléaire de type Bodipy, nous avons préalablement mis au point la synthèse d’un bodipy mononucléaire et nous avons examiné ses propriétés optiques. Nous nous sommes dès lors basé sur les conditions de synthèse de ce bodipy mononucléaire pour tenter de réaliser, sans succès, la synthèse du complexe hétéronucléaire [Ir(ppy)2µdipyBF2].<p>L’ensemble des résultats obtenus au cours de ce travail, nous ont permis de comprendre l’effet du métal de transition et celui de la dérivatisation du dipyrrométhène sur les propriétés photophysiques des complexes formés. Il serait dès lors intéressant de tirer parti de l’ensemble de ces résultats pour mettre au point un nouveau dérivé pontant du dipyrrométhène afin d’optimiser les propriétés des complexes formés, et à terme permettre la préparation de réseaux organométalliques performants et exploitables dans des dispositifs électroluminescents. / Doctorat en Sciences / info:eu-repo/semantics/nonPublished