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

Although attractive interactions between π systems (π-π interaction) have been known for many years, understanding of its origin is still incomplete. Quantitative measuring of π-stacking is challenging due to the weak nature of the π-π interaction. This dissertation aims at elucidating a quantitative conformational analysis by NMR ring current anisotropy of an organic compound capable of intramolecular π-stacking in solution and studying charge effects on the stacking of π-systems. This dissertation offers four contributions to the area. (1) A general approach to four-state, conformational analysis based on the magnetic anisotropy of molecules undergoing fast dynamic exchange is described. (2) Study unveiled the importance of charges in the conformation of a dication in the solution. (3) Novel aromatic salt pairs of triangulene derivatives with the delocalized cation-anion interaction were synthesized and studied. (4) Study unveiled ionic π-systems preferred face-to-face stacking due to strong cation-π and anion-cation attractions. A general protocol for the application of magnetic anisotropy to quantitative multi-state conformational analysis of molecules undergoing fast conformational exchange was suggested in the current study. The reliability of this method of conformational analysis was checked by the mass balance. VT-NMR was also conducted to study the enthalpic parameters. This technique can be further used to study canonical interactions such as ion pairing, hydrogen boning, and molecular recognition. In the current study, dependence of the probe conformations on the dispersive interactions at the aromatic edges between solvent and probes was tested by conformational distributions of the fluorinated derivatives (2b and 2c) of the probe molecule (1a). Solution and solid studies of these molecules put the previous conclusion drawn by the Cammers group in question. Current studies show that the dispersive interaction at the aromatic edge could not be the predominant force on the conformational changes in the probe molecule 1a during the fluoroalkanol perturbation. This study indicated that charges might be important in the formation of the folding conformations in the solution and solid state of 1a, 2b, and 2c. A contribution of this thesis was to prepare and study a conformational model that lacked charges. The previous molecules were charged. The solid-state structures of pyridinium-derived aromatic rings from the CSD (Cambridge Structural Database) were studied to investigate the π-π interaction between cationic π-systems in solid state. Novel aromatic salt pairs of triangulene derivatives with the delocalized cation-anion interaction were synthesized to study the π-π interaction between two aromatic rings that carried opposite charges. This study showed that the interaction between ionic π-systems can be enhanced by cation-π and anion-cation attractions. The stackings of these π-systems introduce more overlap, closer packing and stronger atomic contact than that of the solid states of comparable neutral species. Cation-π and anion-cation attractions are synergistic in aromatic salts.

In this paper we show that pairs of stocks which have a true long run equilibrium (cointegration) yield a higher return than pairs of stocks that relies on a more spurious relationship (correlation) when applying Pairs Trading for a trading period from 31/12-09 to 25/6-14. We get an annual return for the cointegration portfolio of 4,15%, with a Sharpe-ratio of 0,87. For the correlated portfolio we get 2,08% and 0,45, respectively. The Sharpe-ratio for a buy-and-hold market index during the same period was 1,08.

While hundreds of papers have been published on frustrated Lewis pairs (FLPs) – the combination of bulky Lewis acids and bases which cannot form adducts – few of these use aluminum-based Lewis acids. The research outlined in this thesis expands the small molecule activation chemistry of FLPs to include Al.Combinations of bulky phosphines and AlX3 (X = halide or C6F5) with CO2 leads to the rapid activation to form the complexes R3P(CO2)(AlX3)2 (R = otol, Mes). Subsequent treatment with ammonia borane (AB) results in the rapid reduction of the CO2 fragment to methanol after water quench. Subsequent reactivity studies have established that AB adducts of AlX3, which react with CO2, are key intermediates in this chemistry. Further studies with Mes3P(CO2)(AlX3)2 revealed that these can reduce exogenous CO2 to CO, along with the generation of Mes3P(C(OAlX2)2O)(AlX3) and [Mes3PX][AlX4]. Detailed experimental and theoretical mechanistic investigations outline a possible mechanism involving direct CO2 insertion into free AlX3, followed by nucleophilic attack by PMes3 resulting in the expulsion of CO. Reactions with olefins were also investigated. While addition products of the type R3P(CH2CH2)AlX3 could be obtained with ethylene, C–H bond activation occurred with bulkier olefins. The resulting allyl species underwent subsequent C–C bond forming reactions with other olefins or CO2. Hydrogen was also activated using PR3/AlX3 FLPs to form species of the general formula, [R3PH][(H)(AlX3)2] (X = I, C6F5). These were found to reduce unactivated olefins, generating the redistributed products [R3PH][AlX4] and RAlX2 (R = alkyl). Attempts to circumvent this redistribution and favour alkyl protonation, thus generating a catalytic hydrogenation catalyst, are also discussed. Finally, the activation of N2O was also examined. While addition products could be formed, unexpected aromatic or benzylic C–H bond activation chemistry occurred in the presence of excess Al. A radical reaction pathway is proposed

Three classes of bifunctional compounds related to frustrated Lewis pair chemistry were studied. The first class, alkynyl-linked phosphonium borates, was strategically synthesized and the corresponding neutral alkynyl-linked phosphine boranes generated in solution. They were reacted with THF, alkenes and alkynes to undergo either ring-opening or multiple bond addition reactions, giving rise to zwitterionic macrocycles. In two select alkynyl-linked phosphonium borates, thermolysis resulted in unique rearrangements transforming the phosphino- and boryl-substituted alkynyl moieties into C4 chains. The alkynyl-linked phosphine boranes were further demonstrated to coordinate as η3-BCC ligands in Ni(0) complexes. The rigid nature of the coordination was confirmed by dimerization without cleavage of the Ni–B interaction upon the addition of acetonitrile or carbon monoxide. Moreover, reactions with Al-, Zn- and B-based Lewis acids prompted hydride transfer within the alkynyl-linked phosphonium borate and interesting functional group transfer reactions. The second class of the bifunctional systems, a series of gem-substituted bis-boranes, was subjected to reactions with tBu3P and CO2. The O-linked bis-borane was shown to coordinate the phosphino-carboxylate moiety with one B, while the methylene-linked bis-boranes were demonstrated to chelate the carboxyl group. The third bifunctional system class, vinyl-group tethered boranes, was examined to elucidate the mechanism of the frustrated Lewis pair addition reaction to olefins. Using a bis(pentafluorophenyl)alkylborane, the close proximity of the olefinic protons and the ortho-fluorine nuclei were evident by both NOE measurements and DFT calculations. Moreover, its reactions with phosphine bases suggested that an initial interaction between the highly electrophilic borane and the olefinic fragment precedes such frustrated Lewis pair addition reaction. Furthermore, a bis(pentafluorophenyl)alkoxyborane was synthesized and reacted with P-, N-, C- and H-based nucleophiles, demonstrating the wide range of Lewis bases that can be applied in olefin addition reactions with complementary regioselectivity.

While hundreds of papers have been published on frustrated Lewis pairs (FLPs) – the combination of bulky Lewis acids and bases which cannot form adducts – few of these use aluminum-based Lewis acids. The research outlined in this thesis expands the small molecule activation chemistry of FLPs to include Al.Combinations of bulky phosphines and AlX3 (X = halide or C6F5) with CO2 leads to the rapid activation to form the complexes R3P(CO2)(AlX3)2 (R = otol, Mes). Subsequent treatment with ammonia borane (AB) results in the rapid reduction of the CO2 fragment to methanol after water quench. Subsequent reactivity studies have established that AB adducts of AlX3, which react with CO2, are key intermediates in this chemistry. Further studies with Mes3P(CO2)(AlX3)2 revealed that these can reduce exogenous CO2 to CO, along with the generation of Mes3P(C(OAlX2)2O)(AlX3) and [Mes3PX][AlX4]. Detailed experimental and theoretical mechanistic investigations outline a possible mechanism involving direct CO2 insertion into free AlX3, followed by nucleophilic attack by PMes3 resulting in the expulsion of CO. Reactions with olefins were also investigated. While addition products of the type R3P(CH2CH2)AlX3 could be obtained with ethylene, C–H bond activation occurred with bulkier olefins. The resulting allyl species underwent subsequent C–C bond forming reactions with other olefins or CO2. Hydrogen was also activated using PR3/AlX3 FLPs to form species of the general formula, [R3PH][(H)(AlX3)2] (X = I, C6F5). These were found to reduce unactivated olefins, generating the redistributed products [R3PH][AlX4] and RAlX2 (R = alkyl). Attempts to circumvent this redistribution and favour alkyl protonation, thus generating a catalytic hydrogenation catalyst, are also discussed. Finally, the activation of N2O was also examined. While addition products could be formed, unexpected aromatic or benzylic C–H bond activation chemistry occurred in the presence of excess Al. A radical reaction pathway is proposed

This thesis describes various methods for producing photon pairs from waveguides. It covers relevant topics such as waveguide coupling and phase matching, along with the relevant measurement techniques used to infer photon pair production. A new proposal to solve the phase matching problem is described along with two conceptual methods for generating entangled photon pairs. Photon pairs are also experimentally demonstrated from a third novel structure called a Bragg Reflection Waveguide (BRW). The new proposal to solve the phase matching problem is called Directional Quasi-Phase Matching (DQPM). It is a technique that exploits the directional dependence of the non-linear susceptiblity ($\chi^{(2)}$) tensor. It is aimed at those materials that do not allow birefringent phase-matching or periodic poling. In particular, it focuses on waveguides in which the interplay between the propagation direction, electric field polarizations and the nonlinearity can change the strength and sign of the nonlinear interaction periodically to achieve quasi-phasematching. One of the new conceptual methods for generating entangled photon pairs involves a new technique that sandwiches two waveguides from two differently oriented but similar crystals together. The idea stems from the design of a Michelson interferometer which interferes the paths over which two unique photon pair processes can occur, thereby creating entanglement in any pair of photons created in the interferometer. By forcing or sandwiching the two waveguides together, the physical space that exists in the standard Micheleson type interferometer is made non-existent, and the interferometer is effectively squashed. The result is that the two unique photon pair processes actually occupy the same physical path. This benefits the stability of the interferometer in addition to miniaturizing it. The technical challenges involved in sandwiching the two waveguides are briefly discussed. The main result of this thesis is the observation of photon pairs from the BRW. By analyzing the time correlation between two single photon detection events, spontaneous parametric down conversion (SPDC) of a picosecond pulsed ti:sapph laser is demonstrated. The process is mediated by a ridge BRW. The results show evidence for type-0, type-I and type-II phase matching of pump light at 783nm, 786nm and 789nm to down converted light that is strongly degenerate at 1566nm, 1572nm, and 1578nm respectively. The inferred efficiency of the BRW was 9.8$\cdot$10$^{-9}$ photon pairs per pump photon. This contrasts with the predicted type-0 efficiency of 2.65$\cdot$10$^{-11}$. This data is presented for the first time in such waveguides, and represents significant advances towards the integration of sources of quantum information into the existing telecommunications infrastructure.

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Thèses (Ph.D.)--Université de Sherbrooke (Canada), 2004. / Titre de l'écran-titre (visionné le 19 juillet 2006). Publié aussi en version papier.