Radicals; Radical Ions; Closed-shell ions; Matrix Isolation Spectroscopy; Quantum chemical modelling; reactive intermediates; photochemistry; pyrolysis; radiolysis; low temperature IR- and UV/VIS spectroscopy; matrix isolation; quantum chemical calculations
Menon Ambili, Bally Thomas, Radom Leo (2012), nfluence of Connector Groups on the Interactions of Substituents with Carbon-Centered Radicals, in J. Phys. Chem. A
, 116, 10203-10298.
Bloch-Mechkour Anna, Bally Thomas, Yamamoto Takuhei, Chen Pi-Yu, Lin Guanxing, Jacobsen Neil E., Glass Richard S. (2012), Synthesis and rotation barriers in 2, 6-Di-(o-anisyl) anisole, in J. Phys. Org. Chem
, 25, 878-882.
Šolomek Tomáš, Mercier Sébastien, Bally Thomas, Bochet Christian (2012), Photolysis of ortho-nitrobenzylic derivatives: the importance of the leaving group, in Photochem. Photobiol. Sci.
, 11, 548-555.
Menon AS, Henry DJ, Bally T, Radom L (2011), Effect of substituents on the stabilities of multiply-substituted carbon-centered radicals, in ORGANIC & BIOMOLECULAR CHEMISTRY
, 9(10), 3636-3657.
Nunes Claudio M., Reva Igor, Pinha e Melo Teresa M. V. D., Fausto R., Šolomek Tomáš, Bally Thomas (2011), The Pyrolysis of Isoxazole Revisited: A New Primary Product and the Pivotal Role of the Vinylnitrene. A Low-Temperature Matrix Isolation and Computational Study, in J. Am. Chem. Soc.
, 133(46), 18911-18923.
Bloch-Mechkour A, Bally T, Marcinek A (2011), Dimer Radical Cations of Indole and Indole-3-carbinol: Localized and Delocalized Radical Cations of Diindolylmethane, in JOURNAL OF PHYSICAL CHEMISTRY A
, 115(26), 7700-7708.
Bally T, Rablen PR (2011), Quantum-Chemical Simulation of H-1 NMR Spectra. 2. Comparison of DFT-Based Procedures for Computing Proton-Proton Coupling Constants in Organic Molecules, in JOURNAL OF ORGANIC CHEMISTRY
, 76(12), 4818-4830.
Bally Thomas, Rablen Paul (2011), Quantum-Chemical Simulation of 1H NMR Spectra. 2.† Comparison of DFT-Based Procedures for Computing Proton␣Proton Coupling Constants in Organic Molecules, in J. Org. Chem.
, 76, 4818-4830.
Zakai UI, Bloch-Mechkour A, Jacobsen NE, Abrell L, Lin GX, Nichol GS, Bally T, Glass RS (2010), Synthesis and Structure of m-Terphenyl Thio-, Seleno-, and Telluroethers, in JOURNAL OF ORGANIC CHEMISTRY
, 75(24), 8363-8371.
The ability to predict and control the outcome of chemical reactions, be it in biology or technology, frequently requires knowledge of the key reaction intermediates. The present research project focusses on the study of such fleeting species (primarily charged and uncharged radicals as well as closed-shell ions) under conditions where they persist sufficiently long to be probed by conventional spectroscopic means. To this end, suitable precursors are embedded in inert solid media at low temperature where the targeted reactive intermediates may then be generated by photolsis or radiolysis of these precursors. Another approach, mainly for radicals, consists in the pyrolysis of suitable precursors, which has the advantage that the two fragments end up in different matrix cavities and can thus not recombine. The electronic and vibrational spectra of the resulting species contain information that is used to confirm or reject hypotheses with regard to the identity and the structure of reactive intermediates. In addition, their reactivity can be probed by allowing them to rearrange, either by slightly raising the temperature or by exposing them to light at selected wavelengths, or by letting them engage in bimolecular reactions with suitable small reactants with which the host material is doped. A common feature of all projects is, that the experimental work is invariably accompanied by quantum chemical model calculations which serve on the one hand to interpret the spectroscopic observations and on the other hand to shed light on the reactivity of the observed species. Much of the insight obtained in this project arises from a synergy betwen experimental and theoretical approaches.