No description available.

L'adsorption de l'anthracène et de molécules de type Diphényl-polyènes (trans-Stilbene, 1,4-Diphenyl-1,3 butadiene, 1,6-Diphenyl-1,3,5-hexatriene) a été étudiée par simulations Monte Carlo, absorption UV-visible par réflexion diffuse, diffusion Raman multiexcitation et Résonance Paramagnétique Electronique (RPE) dans des zéolithes (aluminosilicates) à canaux de type Ferrierite (M-FER), ZSM-5 (MnZSM-5) et Mordenite (M-MOR).<br />Les résultats mettent en évidence l'insertion des molécules dans les canaux. Dans le cas de cations polarisants (M = H+ et Li+) une ionisation spontanée produit la formation de paires radical cation – électron de longue durée. Au cours de la recombinaison de charges, des paires électron-trou sont mises en évidence par des techniques impulsionnelles de RPE. Dans le cas des molécules insérées sans modification chimique (M = Na+, K+, Rb+, Cs+), la photolyse UV induit des paires de radicaux dont la lente recombinaison implique des phénomènes de transferts d'électrons régis par la théorie de Marcus. L'exceptionnelle stabilité des paires de radicaux est attribuée au confinement des molécules dans les canaux, à la teneur en aluminium et à la nature des cations de la zéolithe. Ces paires de radicaux sont des intermédiaires réactionnels mis en jeu dans les processus catalytiques et de photodégradation d'hydrocarbures. Ils sont aussi impliqués dans le processus primordial de l'effet photovoltaïque.

Diese Arbeit befasst sich mit der vibronischen Kopplung zweier angeregter Elektronenniveaus in Diphenylhexatrien (DPH) und mit der Rolle von Schwingungsmoden beim ultraschnellen photoinduzierten intramolekularen Elektronentransfer in Betain-30. Mit Hilfe von Pikosekunden-zeitaufgelöster Kohärenter Antistokes Ramanspektroskopie im angeregten Zustand des DPH haben wir zum ersten Mal das Auftreten zweier extrem frequenzverbreiterter Ramanlinien beobachtet, die gegenüber dem C=C Streckschwingungsbereich zu höheren Wellenzahlen verschoben sind. Beide Ramanlinien lassen sich mit Erhöhung der Lösungsmittelpolarisierbarkeit um mehr als 50 cm-1 in Richtung niedrigerer Frequenzen verschieben. Zur Erklärung des Sachverhalts werden zwei Modelle diskutiert: (i) die Existenz zweier Isomere im ersten angeregten Elektronenniveau des DPH und (ii) vibronische Kopplung der beiden Elektronenniveaus durch eine niederfrequente asymmetrische bu Schwingungsbewegung (pseudo-Jahn-Teller Effekt). Mit Hilfe von stationärer Ramanspektroskopie und insbesondere Messungen der Stokes- und anti-Stokes-Ramanspektren mit Pikosekunden-Zeitauflösung, die Beteiligung von Molekülschwingungen beim Elektronentransfer in Betain-30 wurde untersucht. Zum ersten Mal wurde eine modenspezifische Kinetik der Ramanaktiven Schwingungen nach Elektronen Rücktransfer in Betain-30 beobachtet. Die hochfrequenten Ramanaktiven Moden werden beim Elektronen Rücktransfer bevorzugt, was zu einer nicht-thermischen Besetzung der Schwingungen führt. Das ist zumindest qualitativ in Übereinstimmung mit Rechnungen die auf Fermi's Goldener Regel basieren. Eine Thermalisierung zwischen den beobachteten Ramanaktiven Moden stellt sich frühestens 10 ps nach Anregung ein. Die Thermalisierung in dem gesamten Molekül ist aber noch nicht beendet. / This thesis deals with vibronic coupling effects between two excited electronic singlet states in Diphenylhexatriene (DPH), and with the role of vibrational modes in photoinduced ultrafast electron transfer in Betaine-30. By using the picosecond time-resolved Coherent Antistokes Raman Spectroscopy method, it was possible to observe for the first time two very broad and unusual up-shifted vibrational frequencies in the excited singlet state of DPH, which have frequencies higher than frequency region of the C=C stretching mode. These two frequencies shift towards lower frequencies with increasing solvent polarizability. Two explanations have been discussed: (i) the simultaneous existence of two rotamers, where the two frequencies originate from "different molecules" and (ii) a model of vibronic coupling by an asymmetric low frequency bu-mode (pseudo-Jahn-Teller effect). By using the picosecond time-resolved anti-Stokes Raman spectroscopy method, we observed for the first time mode-specific excitation of vibrational modes after back-electron transfer in Betaine-30. In the primary event, high frequency Raman active modes are most effective in accepting energy, which leads to a non-thermal distribution of the relative populations of Raman active modes. This is qualitatively in accordance with predictions derived from Fermi's Golden Rule. Although energy transfer between the Raman active modes has been finished after about 10 to 15 ps, thermalization is not yet complete in the whole molecule.

The natural product celastrol (1) possesses a wide array of promising biological activities related to diseases characterized by protein misfolding including those associated with neuronal degradation, inflammation, and cancer. Relevant to cancer, celastrol functions as a non-ATP-competitive inhibitor of heat shock protein-90, providing a potential lead for the development of new inhibitors with improved pharmacology. A laboratory preparation of the small molecule was undertaken to provide access to the unnatural enantiomer of celastrol. The lack of understanding of the chemistry and biology of the growing class of celastroids is attributed to the incompatibility of biologically inspired polyene cyclization strategies to assemble friedelin triterpenoids. As a result of these problems residing at the interface of chemistry and biology, a purely synthesis-based strategy for polyene cyclizations to rapidly construct the pentacyclic core of the friedelin and celastroid natural products has been developed. This efficient strategy is gram scalable culminating in the first total synthesis of wilforic acid (127) and an advanced intermediate capable of delivering celastrol (1) as well as numerous celastroid natural products. Phenols possess broad utility serving as key materials in all facets of chemical industries, especially the pharmaceutical industry. The ideal synthesis of a phenolic compound entails the direct oxidation of an aryl C-H bond remains to be a difficult synthetic challenge. Following our initial report describing the hydroxylation of arenes using phthaloyl peroxide, new peroxide derivatives were investigated to probe their reactivity in an effort to hydroxylate aromatics which were previously unreactive. Electronically poor to moderately rich arenes were successfully hydroxylated with a broad functional group tolerance using 4,5-dichlorophthaloyl peroxide. This protocol has been applied toward the rapid synthesis of phenolic analogs and metabolites of current pharmaceuticals as well as biocides. Mechanistic studies using kinetic isotope effect, competition, and benzylic oxidation experiments indicate that a novel diradical reverse-rebound mechanism is the likely pathway. Further examination of the transition-state using linear free energy relationships with sigma vs. sigma+ values established a linear trend with a low negative rho value (- 3.92) corresponding best using sigma values supporting a diradical reverse-rebound addition. / text

No description available.

The present thesis deals with a theoretical study of electronic structures in -conjugated molecular materials with focus on their application in organic elec-tronics. We also discuss a modified and efficient symmetrized DMRG algorithm for studying excited states in these systems. In recent times, organic conjugated systems have emerged as potential candidates in a wide range of fascinating fields by virtue of their tunable electronic properties, easy processability and low cost. Tunability in the electronic and optical properties primarily are centered on the or-dering and nature of the low-lying excited states. Probing these important excited states also demands development of efficient and adaptable techniques. Chapter 1 provides a basic overview of conjugated organic polymers which have been utilized over decades in diverse fields as in organic light emitting diodes (OLED), organic solar cells (OSC) and non-linear optical (NLO) devices. These systems also contribute significantly to theoretical understanding as they pro vide important insights of one and quasi-one dimensional systems. In this chapter, we have given basic description of the electronic processes in OLED and OSC along with a brief theoretical description of -conjugated organic systems. Chapter 2 gives an account of the numerical techniques which are necessary for the study of low-dimensional strongly correlated systems like -conjugated sys-tems. For this purpose, effective low-energy model Hamiltonians viz. Huckel,¨ Hubbard and Pariser-Parr-Pople Hamiltonians are discussed. Exact diagonalization technique within the diagrammatic valence bond (DVB) basis and density matrix renormalization group (DMRG) technique are discussed in details. We have also given brief accounts of the methods employed to study real-time dynamics. A short description of different computational techniques for the study of NLO properties in -conjugated systems is also provided. Engineering the position of the lowest triplet state (T1) relative to the first excited singlet state (S1) is of great importance in improving the efficiencies of organic light emitting diodes and organic photovoltaic cells. In chapter 3, we have carried out model exact calculations of substituted polyene chains to understand the fac-tors that affect the energy gap between S1 and T1. The factors studied are backbone dimerization, different donor-acceptor substitutions and twisted backbone geome-try. The largest system studied is an eighteen carbon polyene which spans a Hilbert space of about 991 million in the triplet subspace. We show that for reverse inter-system crossing (RISC) process, the best choice involves substituting all carbon sites on one half of the polyene with donors and the other half with acceptors. Singlet fission (SF) is a potential pathway for significant enhancement of efficiency in OSC. In chapter 4, we study singlet fission in a pair of polyene molecules in two different stacking arrangements employing exact many-body wave packet dy-namics. In the non-interacting model, SF is absent. The individual molecules are treated within Hubbard and Pariser-Parr-Pople (PPP) models and the interac-tion between them involves transfer terms, intersite electron repulsions and site-charge—bond-charge repulsion terms. Initial wave packet is construc ted from ex-cited singlet state of one molecule and ground state of the other. Time develop-ment of this wave packet under the influence of intermolecular interactions is fol-lowed within the Schrodinger¨ picture by an efficient predictor-corrector scheme. In unsubstituted Hubbard and PPP chains, 21A state leads to significant SF yield while the 11B state gives negligible fission yield. On substitution by donor-acceptor groups of moderate strength, the lowest excited state will have sufficient 2 1A char-acter and hence gives significant SF yield. Because of rapid internal c onversion, the nature of the lowest excited singlet will determine the SF contribution to OSC effi - ciency. Furthermore, we find the fission yield depends considerably on th e stacking arrangement of the polyene molecules. In chapter 5, we have given an account of a new modified algorithm for symmetry adaptation within symmetrized density matrix renormalization group (SDMRG) technique. SDMRG technique has been an efficient method for studying low-lying eigenstates in one and quasi-one dimensional electronic systems. However, SDMRG method until now, had bottlenecks involving construction of linearly in-dependent symmetry adapted basis states as the symmetry matrices in the DMRG basis were not sparse. Our modified algorithm overcomes this bottleneck. T he new method incorporates end-to-end interchange symmetry (C2), electron-hole symmetry (J) and parity or spin-flip symmetry (P) in these calculations. The one-to-one correspondence between direct-product basis states in the DMRG Hilbert space for these symmetry operations renders the symmetry matrices in the new ba-sis with maximum sparseness, just one non-zero matrix element per row. Using methods similar to those employed in exact diagonalization technique for Pariser-Parr-Pople (PPP) models, developed in the eighties, it is possible to construct or-thogonal SDMRG basis states while bypassing the slow step of Gram-Schmidt orthonormalization procedure. The method together with the PPP model which incorporates long-range electronic correlations is employed to study the correlated excited states of 1,12-benzoperylene. In chapter 6, we have studied the correlated excited states of coronene and ova-lene within Pariser-Parr-Pople (PPP) model employing symmetry adapted density matrix renormalization group technique. These polynuclear aromatic hydrocar-bons can be considered as graphene nanoflakes and study of their ele ctronic struc-tures will shed light on the electron correlation effects in these finite-size gr aphene analogues. The electron correlation effect usually diminishes on going from one-dimensional to higher-dimensional systems, yet, it is significant within these fin ite-size graphene derivatives where it depends on the molecular topology. We have characterized these low-lying energy states by calculating bond orders, spin den-sities in the lowest triplet state and two-photon absorption cross-sections for low-lying two-photon states. vi

PhD (Department of Chemistry, Faculty of Applied and Computer Sciences), Vaal University of Technology. / This research has investigated the effects of conjugation on the visible light absorption capacity of polyene modified TiO2 nanoparticles as well as the efficiency of these nanoparticles for the mineralisation of acetaminophen (APAP), a non-antibiotic and chloramphenicol (CAP), an antibiotic pharmaceutical compound (PC) which are commonly used worldwide. The efficiency of polyene modified TiO2 (CPE-TiO2) compared with bare TiO2 was further assessed for the mineralisation of the selected PCs under visible light. To achieve this aim, the synthesised nanoparticles were appropriately characterised and tested for the photocatalytic degradation of acetaminophen (APAP) and chloramphenicol (CAP), under visible light. Furthermore, the mechanism and the kinetics of photocatalytic degradation of the PCs were investigated by using high-performance liquid chromatography (HPLC) to monitor the photodegradation intermediates, e.g. Hydroquinone, p-nitrophenol and oxamic acid. The DRS UV-vis spectra result of the CPE-TiO2 indicated that it has a lower band-gap than bare TiO2 nanoparticles and demonstrated a better absorption ability in the wavelength range of 400-800 nm. This result was further confirmed by other optical analyses, such as electrochemical impedance spectrometry (EIS) and photoluminescence (PL). The analysis indicated a less recombination rate of electron/hole pairs in CPE-TiO2 compared to TiO2. Notably, CPE-TiO2 nanocomposite exhibited higher photocatalytic properties for both pollutants, compared to bare TiO2 under visible light. Importantly, photocatalytic degradation experiments demonstrated that the CPE modified nanoparticles were significantly more efficient for PCs degradation (94.21 % for APAP and 80.47% for CAP) compared to bare TiO2 (27.12% for APAP and 36.12% for CAP). The role of CPE-TiO2 photocatalysis in degrading APAP and CAP was examined by varying experimental parameters such as PC concentrations, catalyst loading and solution pH. All the parameters were observed to influence the degradation of the PCs to some extent, albeit, at optimum conditions, most of these PCs were degraded within 210 minutes of visible light irradiation. A significant relationship between the ionic state (+ve or -ve based on the pH) of the solution and CPE-TiO2 photocatalytic process was observed. For the mineralisation, CPE-TiO2 photocatalysis led to higher oxidation rates compared to direct photolysis and bare TiO2 photocatalysis. The results confirm that the co-existence of multiple bonds in poly-conjugated carbon chains with a reduced band-gap in CPE-TiO2 composite were able to enhance charge separation and migration as well as improve the photocatalytic efficiency. This study has clearly demonstrated that polyene modified TiO2 nanoparticles can be applied to degrade PCs in aqueous solution and offers an attractive option for small-scale pharmaceutical wastewater treatment. However, the complex nature of real effluents with co-existing pollutants and higher levels of organic and inorganic matter may call for possible coupling of a biological process as pre- or post-treatment to improve their biodegradability.