A Mechanistic Study of Halogen Addition and Photoelimination from ?-Conjugated Tellurophenes

The ability to drive reactivity using visible light is of importance for many disciplines of chemistry and has significant implications for sustainable chemistry. Identifying photochemically active compounds and understanding photochemical mechanisms is important for the development of useful materials for synthesis and catalysis. Here we report a series of photoactive diphenyltellurophene compounds bearing electron-withdrawing and electron-donating substituents synthesized by alkyne coupling/ring closing or palladium-catalyzed ipso-arylation chemistry. The redox chemistry of these compounds was studied with respect to oxidative addition and photoelimination of bromine, which is of importance for energy storage reactions involving X₂. The oxidative addition reaction mechanism was studied using density functional theory, the results of which support a three-step mechanism involving the formation of an initial η¹ association complex, a monobrominated intermediate, and finally the dibrominated product. All of the tellurophene derivatives undergo photoreduction using 430, 447, or 617 nm light depending on the absorption properties of the compound. Compounds bearing electron-withdrawing substituents have the highest photochemical quantum efficiencies in the presence of an alkene trap, with efficiencies of up to 42.4% for a pentafluorophenyl-functionalized tellurophene. The photoelimination reaction was studied in detail through bromine trapping experiments and laser flash photolysis, and a mechanism is proposed. The photoreaction, which occurs by release of bromine radicals, is competitive with intersystem crossing to the triplet state of the brominated species, as evidenced by the formation of singlet oxygen. These findings should be useful for the design of new photochemically active compounds supported by main-group elements

Photochemistry and photophysics of thienocarbazoles

Two methylated thienocarbazoles and two of their synthetic nitro-precursors have been examined by absorption, luminescence, laser flash photolysis and photoacoustic techniques. Their spectroscopic and photophysical characterization involves fluorescence spectra, fluorescence quantum yields and lifetimes, and phosphorescence spectra and phosphorescence lifetimes for all the compounds. Triplet-singlet difference absorption spectra, triplet molar absorption coefficients, triplet lifetimes, intersystem crossing S-1 similar tosimilar to--> T-1 and singlet molecular oxygen yields were obtained for the thienocarbazoles. In the case of the thienocarbazoles it was found that the lowest-lying singlet and triplet excited states, S, and T-1, are of pi,pi* origin, whereas for their precursors S-1 is n,pi*, and T-1 is pi,pi*. In both thienocarbazoles it appears that the thianaphthene ring dictates the S, T, yield, albeit there is less predominance of that ring in the triplet state of the linear thienocarbazole, which leads to a decrease in the observed Phi(T) value.info:eu-repo/semantics/publishedVersio

Temperature Dependence of Solar Light Assisted CO2 Reduction on Ni Based Photocatalyst

Methanation of CO2 by H-2 can be in the future an important reaction to store the surplus of renewable electricity during production peaks. The catalytic thermal CO2 methanation (the Sabatier reaction) can be carried out at temperatures above 250 degrees C using Ni supported on silica-alumina (Ni/SiO2-Al2O3). Recently it has been observed that this exothermic reaction can be promoted by solar light irradiation of Ni/SiO2-Al2O3 at initial near ambient temperatures. In the present work we provide a study of the influence of the initial temperature on the photoassisted Ni/SiO2-Al2O3 methanation of CO2, under conditions in which the dark reaction is not observed. An increase of the photoassisted methanation rate with the initial temperature in the range from ambient to 150 degrees C has been observed. The reaction kinetics for lower initial temperatures exhibited an induction period not observed for reactions performed at higher temperatures. The results are discussed in terms of the operation of plasmon photo activation in which the energy of photons is thermalised in a confined space of the active nanoparticles leading to locally high temperatures and the simultaneous photogeneration of electrons and positive holes.Albero Sancho, J.; García Gómez, H.; Corma Canós, A. (2016). Temperature Dependence of Solar Light Assisted CO2 Reduction on Ni Based Photocatalyst. Topics in Catalysis. 59(8-9):787-791. doi:10.1007/s11244-016-0550-xS787791598-9Hammarstrom L, Hammes-Schiffer S (2009) Artificial photosynthesis and solar fuels. Acc Chem Res 42:1859–1860Schlögl R (2015) The revolution continues: energiewende 2.0. Angew Chem Int Ed 54:4436–4439Herron JA, Kim J, Upadhye AA, Huber GW, Maravelias CT (2015) A general framework for the assessment of solar fuel technologies. Energy Environ Sci 8:126–157Hoekman SK, Broch A, Robbins C, Purcell R (2010) CO2 recycling by reaction with renewably-generated hydrogen. Int J Greenh Gas Control 4:44–50Hoch LB, Wood TE, O’Brien PG, Liao K, Reyes LM, Mims CA, Ozin GA (2014) The rational design of a single-component photocatalyst for gas-phase CO2 reduction using both UV and visible light. Adv Sci 1:1400010–1400013Sastre F, Puga AV, Liu L, Corma A, Garcia H (2014) Complete photocatalytic reduction of CO2 to methane by H2 under solar light irradiation. J Am Chem Soc 136:6798–6801Melsheimer J, Guo W, Ziegler D, Wesemann M, Schlögl R (1991) Methanation of carbon dioxide over Ru/titania at room temperature: explorations for a photoassisted catalytic reaction. Catal Lett 11:157–168O’Brien PG, Sandhel A, Wood TE, Jelle AA, Hoch LB, Perovic DD, Mims CA, Ozin GA (2014) Photomethanation of gaseous CO2 over Ru/silicon nanowire catalysts with visible and near-infrared photons. Adv Sci 1:1400001–1400007Ghuman KK, Wood TE, Hoch LB, Mims CA, Ozin GA, Singh CV (2015) Illuminating CO2 reduction on frustrated Lewis pair surfaces: investigating the role of surface hydroxides and oxygen vacancies on nanocrystalline In2O3−x(OH)y. Phys Chem Chem Phys 17:14623–14635Wei W, Jinlong G (2011) Methanation of carbon dioxide: an overview. Front Chem Sci Eng 5:2–10Scaiano JC, Stamplecoskie K (2013) Can surface plasmon fields provide a new way to photosensitize organic photoreactions? Custom applications. J Phys Chem Lett 4:1177–1187Fasciani C, Alejo CJB, Grenier M, Netto-Ferreira JC, Scaiano JC (2011) High-temperature organic reactions at room temperature using plasmon excitation: decomposition of dicumyl peroxide. Org Lett 13:204–207Leadbeater NE (2010) Microwave heating as a tool for sustainable chemistry. CRC Press, Boca Rato

Biological effects of exposure to magnetic resonance imaging: an overview

The literature on biological effects of magnetic and electromagnetic fields commonly utilized in magnetic resonance imaging systems is surveyed here. After an introduction on the basic principles of magnetic resonance imaging and the electric and magnetic properties of biological tissues, the basic phenomena to understand the bio-effects are described in classical terms. Values of field strengths and frequencies commonly utilized in these diagnostic systems are reported in order to allow the integration of the specific literature on the bio-effects produced by magnetic resonance systems with the vast literature concerning the bio-effects produced by electromagnetic fields. This work gives an overview of the findings about the safety concerns of exposure to static magnetic fields, radio-frequency fields, and time varying magnetic field gradients, focusing primarily on the physics of the interactions between these electromagnetic fields and biological matter. The scientific literature is summarized, integrated, and critically analyzed with the help of authoritative reviews by recognized experts, international safety guidelines are also cited

A review on radiation-induced nucleation and growth of colloidal metallic nanoparticles

This review presents an introduction to the synthesis of metallic nanoparticles by radiation-induced method, especially gamma irradiation. This method offers some benefits over the conventional methods because it provides fully reduced and highly pure nanoparticles free from by-products or chemical reducing agents, and is capable of controlling the particle size and structure. The nucleation and growth mechanism of metallic nanoparticles are also discussed. The competition between nucleation and growth process in the formation of nanoparticles can determine the size of nanoparticles which is influenced by certain parameters such as the choice of solvents and stabilizer, the precursor to stabilizer ratio, pH during synthesis, and absorbed dose

Substituent Effect on the Photoreduction Kinetics of Benzophenone

The kinetics of the photoreduction of four benzophenone derivatives by isopropyl alcohol was examined in acetonitrile, namely tetra-meta-trifluoromethyl-, di-para-trifluoromethyl-, di-para-methoxy benzophenone and for comparison the unsubstituted molecule itself. The basic spectroscopic (absorption and phosphorescence spectra) and photophysical (quantum yields, excited state energies) properties were established, and the key kinetic parameters were determined by the laser flash photolysis transient absorption technique. The rate coefficients of both the primary and secondary photoreduction reaction show remarkable dependence on ring substitution. This substantial effect is caused by the considerable change in the activation energy of the corresponding process. The experimental results as well as DFT quantum chemical calculations clearly indicate that these benzophenone derivatives all react as n-p* excited ketones, and the rate as well as the activation energy of the reduction steps change parallel with the reaction enthalpies, the determining factor being the stability of the forming aromatic ketyl radicals. The secondary photoreduction of benzophenones by the aliphatic ketyl radical formed in the primary step occurs via a hydrogen bonded complex. The binding energy of the hydrogen bonded complex between the aliphatic ketyl radical reactant and a solvent molecule is a critical parameter influencing the observable rate of the secondary photoreduction