Dendritic encapsulation of poly(phenyleneethynylene)s or PPEs has been shown to enhance photoluminescent quantum efficiency and facilitate energy transfer by funneling photonic energy absorbed on the dendron periphery efficiently to the conjugated polymeric core. The research presented herein focuses on incorporating degradable dendron onto PPEs, examining whether or not similar benefits were conferred upon the proposed system and controlling polymer luminescence through the elimination of the insulating macromolecules. PPEs appended with disassembling dendrons of various generation sizes were synthesized and their optical properties studied. Polymer luminescence was then quenched via chemical degradation of the disassembling dendrons. Furthermore, the macromolecules resulting from disassembly exhibited tunable luminescence properties upon manipulation of pH. Consequently, it was determined that polymer luminescence could be controlled upon forming phenolic moieties along the PPE backbone. Tunable emission was later realized in the thin film as well through the integration of crosslinkable dendrons onto the polymer core.Recently, helical synthetic linear polymers have demonstrated the ability to facilitate stereoselective processes such as catalysis, recognition and separation. Consequently, it has become increasingly desirable to develop new platforms capable of imparting asymmetry. The work presented herein describes the synthesis of a series of polymers based upon chiral hydrobenzoin and the subsequent conformational analysis performed on these materials. It was envisioned that these polymeric materials might inherently possess conformational asymmetry and as result could be able to impart configurationally chirality by introducing a diastereomeric bias for the formation of one enantiomer over the other during the course of the reaction.

The objective of this thesis is to explore new reactivities and to improve luminescent properties of 7-azaindole-containing metal complexes. Selectivity for the activation of toluene and ethyl benzene has been investigated with two cationic Pt(II)(N,N-L) complexes, where N,N-L = 1,2-bis(1-N-7-azaindolyl)benzene (BAB) or bis(1-N-7-azaindolyl)methane (BAM). A high regioselectivity toward toluene and ethyl benzene benzylic C-H activation and a distinct diastereoselectivity for ethyl benzene benzylic C-H activation are demonstrated. Detailed mechanistic studies have been performed, leading to the establishment of both the intermediacy of the η3-benzylic Pt(II) complexes in the reactions and the ligand steric impacts as origins for the distinct diastereoselectivity. A PtMe2 complex of 1-N-(pyridin-2-yl)-7-azaindole (NPA) has been synthesized and found to undergo facile transformation at ambient temperature, resulting in the quantitive formation of a neutral Pt4 molecular square. The mechanism of the transformation process has been examined, establishing a distinct intramolecular C-H driven self-assembly process. The geometrical impacts of the BAB and BAM ligands on the structure and stability of their fac-Pt(IV)Me3 complexes has been investigated. The BAB ligand is more effective than the BAM ligand in stabilizing the five-coordinate Pt(IV)Me3 complexes. With the BAB ligand, a five-coordinate fac-Pt(IV)Me3 complex is obtained; with the BAM ligand, two six-coordinate fac-Pt(IV)Me3 complexes are obtained. In solution, the methyl groups in the BAB complex exchange slowly, but those in the BAM complexes exchange rapidly. Several new 7-azaindolyl derivative ligands via either modifying or altering the BAM and BAB bridging groups have been developed. The syntheses, structures and reactivities of their Pt(II) complexes have been examined, leading to the finding of an unconventional C-Sn oxidative addition reaction. The modification of the NPA ligand via the incorporation of a triarylboron group has been carried out. Several novel Pt(II) and Cu(I) complexes have been synthesized and studied. A Cu(I) complex is found to display exceptionally bright ambient temperature phosphorescence. A series of dinuclear Cu(I) compounds of the 1,2,3,4-tetra(1-N-7-azaindolyl)benzene (TTAB) ligand have been synthesized and examined. The close contacts between the TTAB bridging phenyl ring and the Cu(I) centers are present in the complexes. / Thesis (Ph.D, Chemistry) -- Queen's University, 2008-05-21 18:10:58.628

The objective of this thesis is to examine the photophysical and structural properties of Cu(I) complexes of 2-(2’-pyridyl)benzimidazolyl based ligands and Cu(I), Pd(II) and Pt(II) complexes of 2-(2’-pyridyl)indolyl based ligands, for possible use as phosphorescent emitters in OLEDs. The discovery of the atropisomeric 3,3’-bis(2-(2’-pyridyl)indolyl based ligands led to the examination of C-C coupling reactions and the investigation of the new chiral ligands with transition metal ions. Cu(I) complexes of 2-(2’pyridyl)benzimidazolyl-benzene with varying phosphine ligands were prepared. The structures were studied with X-ray crystallography and NMR. Experimental and computational results established that steric and electronic properties of the phosphine ligands influence the photophysical properties of the Cu(I) complexes. Polynuclear Cu(I) complexes with 2-(2’-pyridyl)benzimidazolyl based ligands and two PPh3 ancillary ligands were synthesized, the photoluminescent and electroluminescent properties were examined. A series of 2-(2’-pyridyl)indolyl based ligands; 2-(2’-pyridyl)indolyl-benzene (pib), 1,4-bis[2-(2’-pyridyl)indolyl]benzene (bib) and 1,3,5-tris[2-(2’-pyridyl)indolyl]benzene) (tib) and the corresponding C-C coupled dimers bis[3,3’(2-(2’-pyridyl)indolyl-benzene)] (bpib), bis[3,3’(1,4-bis[2-(2’-pyridyl)indolyl]benzene (bbib) and bis[3,3’(1,3,5-tris[2-(2’-pyridyl)indolyl]benzene)] (btib) were synthesized in a one-pot reaction with the formation of both C-N and C-C bonds. The photophysical properties of these new molecules were investigated. The dimers display intramolecular exciplex formation. The rotation barrier around the C-C bond in the 3 position of the bis-indole was calculated using DFT which support that bpib is an atropisomeric ligand. Cu(I), Pd(II) and Pt(II) complexes were synthesized with pib and bpib. [Cu(pib)(PPh3)2]+ contains a three-coordinate Cu(I) ion and doesn’t display MLCT but rather 3π-1π phosphorescence. In Pd(pib)(acac) and Pt(pib)(DMSO)Cl the pib ligand forms C,N chelated neutral complexes that display red emission in frozen solution and in solid state. The X-ray crystal structure for [Cu(bpib)2]+ revealed a homo-chiral crystal and for Pd(bpib)Cl2 and Pt(bpib)Cl¬2 show a trans-chelating geometry around the metal centre. Frozen solutions of [Cu(bpib)2]+ and Pd(bpib)Cl2 display MCLT phosphorescence. Finally the atropisomeric ligands bpib and bbib were examined as sensors to determine the enantiomeric excess of Zn(2-bromo-3-methylbutyrate)2 by CD spectroscopy. CD and fluorescent titration experiments verified that these ligands have selective interactions with different Zn(II) carboxylates. DFT computations showed that diastereomeric excess caused by chiral discrimination leads to the CD spectral-response of the atropisomeric ligands toward chiral Zn(II) carboxylates. / Thesis (Ph.D, Chemistry) -- Queen's University, 2008-09-25 09:54:21.464

This thesis describes the examination of novel block copolymers that contain Ru(bpy)32+ complexes incorporated into one block of diblock copolymers made by ROMP. With the intent of exploring the potential usefulness of these interesting materials in applications such as light-harvesting and sensing, a systematic study of the solution self-assembly, luminescence properties, and the ability of the metal complex to engage in electron and energy transfer reactions has been conducted. / The solution self-assembly of block copolymers that contain Ru(bpy) 32+ complexes was examined first. Using a series of these block copolymers, a detailed study of the effects of block length, block ratio, polymer concentration and solution conditions on the copolymer self-assembly is presented. Using TEM, a number of morphologies were reproducibly observed including star micelles, large compound micelles, tubules, and interestingly, vesicles. These structures all contain the metal complex Ru(bpy)3 2+ within their core domains. / The luminescence properties of two block copolymers containing Ru(bpy) 32+ were examined: one polymer self-assembled into star micelles, the other into vesicles. Comparison of the unassembled polymer chains and the self-assembled polymers indicated that self-assembly, and confinement of the Ru(bpy)32+ complexes into the core domains of the aggregates, did not seriously adversely affect the luminescence properties of the metal complex. Measurement of the luminescence lifetime decay of the polymers suggested that energy migration occurred among the metal complexes along the polymer chain. The ability of the metal complexes within self-assembled structures to participate in electron transfer reactions with small molecules was also explored. It was found that from within the core domains of self-assembled structures, the Ru(bpy)32+ complexes could still engage in electron transfer reactions with molecules on the outsides or the insides of the aggregates, likely a result of energy migration. / The ability of Ru(bpy)32+ complexes within the cores of micelles to participate in energy transfer was explored. Micelles were formed in aqueous solutions using polymers that possessed both the metal complex and a water-soluble block. Several methods were attempted to encapsulate two molecules, a derivative of coumarin 2 and an Os(bpy)3 2+-based molecule, inside these micelles. It was observed that Ru(bpy) 32+ could act as an energy acceptor from the coumarin derivative, and could act as an energy donor to the osmium-based complex. Encapsulation of the small molecules greatly enhanced the efficiency of energy transfer, by non-covalently bringing the small molecules in close proximity to the Ru(bpy)32+ complexes. / Polymers were synthesized that contained a Ru(bpy)3 2+-based block and were terminated with the molecular recognition unit biotin. These polymers, upon self-assembly, formed micelles with biotin groups on their periphery. The addition of the protein streptavidin, which has a strong binding affinity for biotin, resulted in the aggregation of the self-assembled structures. This established the potential for self-assembled metal-containing aggregates to form higher-order structures. / Early work is presented in Appendix A involving block copolymers that contain hydrogen-bonding groups. Several methods were attempted to elucidate the solution morphologies of these polymers, namely IR, 1H NMR, DLS, and pyrene fluorescence. The transition of this initial work to polymers that contain the Ru(bpy)32+ complex is also described.

Thèse numérisée par la Division de la gestion de documents et des archives de l'Université de Montréal

Mémoire numérisé par la Division de la gestion de documents et des archives de l'Université de Montréal

Compositionally related glasses and ceramics of the Na$ sb2$O$ cdot$CaO$ cdot$Al$ sb2$O$ sb3 cdot$TiO$ sb2 cdot$SiO$ sb2$ system (sphene glass-ceramics) doped with Eu$ sp{3+}$ were examined using site-selective spectroscopic techniques (FLN). In sphene glass-ceramics, Eu$ sp{3+}$ preferentially partitions into the crystalline sphene phase. The partition ratio is concentration dependent, decreasing at higher concentrations, because of the limited solid solubility of Eu$ sp{3+}$ in sphene. The concentration occurs at the time of phase separation; Eu$ sp{3+}$ preferentially enters the more ionic (CaO, TiO$ sb2$)- rich droplet phase which eventually becomes sphene. In sphene, Eu$ sp{3+}$ substitutes for Ca$ sp{2+}$ appearing in three different sites caused by associated charge compensation defects. From an analysis of the FLN spectra of the different glasses, the framework for a model describing the coordination shell of Eu$ sp{3+}$ in oxide glasses is developed. The model suggests that Eu$ sp{3+}$ behaves as a network forming ion or quasi-molecular complex. The model is used to explain qualitative features of Eu$ sp{3+}$ FLN spectra including the dependence of the clustering of points of the major crystal field parameter ratios plot on the relative number of non-bridging oxygen ions and Eu$ sp{3+}$ ions in the glass.

In this thesis, luminescence properties of ZnO nanostructures (nanorods, nanotubes, nanowalls and nanoflowers) are investigated by different approaches for possible future application of these nanostructures as white light emitting diodes. ZnO nanostructures were grown by different growth techniques on different p-type substrates. Still it is a challenge for the researchers to produce a stable and reproducible high quality p-type ZnO and this seriously hinders the progress of ZnO homojunction LEDs. Therefore the excellent properties of ZnO can be utilized by constructing heterojunction with other p-type materials. The first part of the thesis includes paper I-IV. In this part, the luminescence properties of ZnO nanorods grown on different p-type substrates (GaN, 4H-SiC) and different ZnO nanostructures (nanorods, nanotubes, nanoflowers, and nanowalls) grown on the same substrate were investigated. The effect of the post-growth annealing of ZnO nanorods and nanotubes on the deep level emissions and color rendering properties were also investigated. In paper I, ZnO nanorods were grown on p-type GaN and 4H-SiC substrates by low temperature aqueous chemical growth (ACG) method. The luminescence properties of the fabricated LEDs were investigated at room temperature by electroluminescence (EL) and photoluminescence (PL) measurements and consistency was found between both the measurements. The LEDs showed very bright emission that was a combination of three emission peaks in the violet-blue, green and orange-red regions in the visible spectrum. In paper II, different ZnO nanostructures (nanorods, nanotubes, nanoflowers, and nanowalls) were grown on p-GaN and the luminescence properties of these nanostructures based LEDs were comparatively investigated by EL and PL measurements. The nanowalls structures were found to be emitting the highest emission in the visible region, while the nanorods have the highest emissions in the UV region due to its good crystal quality. It was also estimated that the ZnO nanowalls structures have strong white light with the highest color rendering index (CRI) of 95 with correlated color temperature (CCT) of 6518 K. In paper III, we have investigated the origin of the red emissions in ZnO by using post-growth annealing. The ZnO nanotubes were achieved on p-GaN and then annealed in different ambients (argon, air, oxygen and nitrogen) at 600 oC for 30 min. By comparative investigations of EL spectra of the LEDs it was found that more than one deep level defects are involved in the red emission from ZnO nanotubes/p-GaN LEDs. It was concluded that the red emission in ZnO can be attributed to oxygen interstitials (Oi) and oxygen vacancies (Vo) in the range of 620 nm (1.99 eV) to 690 nm (1.79 eV) and 690 nm (1.79 eV) to 750 nm (1.65 eV), respectively. In paper IV, we have investigated the effect of post-growth annealing on the color rendering properties of ZnO nanorods based LEDs. ZnO nanorods were grown on p-GaN by using ACG method. The as grown nanorods were annealed in nitrogen, oxygen, argon, and air ambients at 600 oC for 30 min. The color rendering indices (CRIs) and correlated color temperatures (CCTs) were estimated from the spectra emitted by the LEDs. It was found that the annealing ambients especially air, oxygen, and nitrogen were found to be very effective. The LEDs based on nanorods annealed in nitrogen ambient, have excellent color rendering properties with CRIs and CCTs of 97 and 2363 K in the forward bias and 98 and 3157 K in the reverse bias. In the 2nd part of the thesis, the junction temperature of n-ZnO nanorods based LEDs at the built-in potential was modeled and experiments were performed to validate the model. The LEDs were fabricated by ZnO nanorods grown on different p-type substrates (4H-SiC, GaN, and Si) by the ACG method. The model and experimental values of the temperature coefficient of the forward voltage near the built-in potential (~Vo) were compared. It was found that the series resistance has the main contribution in the junction temperature of the fabricated devices. In the 3rd part of the thesis, the influence of helium (He+) ion irradiation bombardment on luminescence properties of ZnO nanorods based LEDs were investigated. ZnO nanorods were grown by the vapor-liquid-solid (VLS) growth method. The fabricated LEDs were irradiated by using 2 MeV He+ ions with fluencies of ~ 2×1013 ions/cm2 and ~ 4×1013 ions/cm2. It was observed that the He+ ions irradiation affects the near band edge emissions as well as the deep level emissions in ZnO. A blue shift about 0.0347 eV and 0.082 eV was observed in the PL spectra in the near band emission and green emission, respectively. EL measurements also showed a blue shift of 0.125 eV in the broad green emission after irradiation. He+ ion irradiation affects the color rendering properties and decreases the color rendering indices from 92 to 89.

Geomorphic, structural and chronological data are used to establish the late Quaternary paleoseismicity of the active dextral-oblique Northern Esk Fault in North Canterbury, New Zealand. Detailed field mapping of the preserved c. 35 km of surface traces between the Hurunui River and Ashley Head reveals variations in strike ranging from 005° to 057°. Along with kinematic data collected from fault plane striae and offset geomorphic markers along the length of the fault these variations are used to distinguish six structural subsections of the main trace, four dextral-reverse and two dextral-normal. Displacements of geomorphic markers such as minor streams and ridges are measured using differential GPS and rangefinder equipment to reveal lateral offsets ranging from 3.4 to 23.7 m and vertical offsets ranging from < 1 to 13.5 m. Characteristic single event displacements of c. 5 m and c. 2 m have been calculated for strike-slip and reverse sections respectively. The use of fault scaling relationships reveals an anomalously high displacement to surface rupture length ratio when compared to global data sets. Fault scaling relationships based on width limited ruptures and magnitude probabilities from point measurements of displacement imply earthquake magnitudes of Mw 7.0 to 7.5. Optically Stimulated Luminescence (OSL) ages from displaced Holocene alluvial terraces at the northern extent of the active trace along with OSL and radiocarbon samples of the central sections constrain the timing of the last two surface rupturing events (11.15 ±1.65 and 3.5 ± 2.8 ka) and suggest a recurrence interval of c. 5612 ± 445 years and late Quaternary reverse and dextral slip rates of c. 0.31 mm/yr and 0.82 mm/yr respectively. The results of this study show that the Northern Esk Fault accommodates an important component of the c. 0.7 – 2 mm/yr of unresolved strain across the plate boundary within the North Canterbury region and affirm the Esk Fault as a source of potentially damaging ground shaking in the Canterbury region.

Barley protoplasts were shown to be a suitable experimental system for studies on the relative maximum during the decay of luminescence observed in most photosynthetic systems after excitation with far red light and in the presence of O2. The far red induced relative luminescence maximum was shown to be a result of three coinciding events: *Randomization of the S-states of the water splitting system during illumination with far red light. *Extreme oxidation of the PSII acceptor side after excitation with far red light and in the presence of O2. *Reverse coupling, causing partial re-reduction of the PSII acceptor side in the dark after far red illumination. When the CO2 concentration in the air above an intact barley leaf was lowered in the dark, the primary PSII acceptor QA was partially reduced. The effect was obtained by changes in CO2 over a wide concentration range including that of saturated photosynthesis. It was thus concluded that the effect was not related to the role of CO2 as the terminal electron acceptor in photosynthesis. White light induced relative maxima during the decay of luminescence frqm low CO2 adapted green algae were shown to be the result of either one or two interacting mechanisms: *Relaxation of qE quenching. *Dark reduction of QA occuring as a result of lowered internal Cj concentration in the dark. Far red induced luminescence decay kinetics and fluorescence induction kinetics, when analyzed with multivariat data analysis, were shown to contain information allowing prediction of the state of frost hardiness in artificially hardened seedlings of Scots pine. / <p>Diss. (sammanfattning) Umeå : Umeå universitet, 1988, härtill 8 uppsatser.</p> / digitalisering@umu