Associate Professor of Chemistry
Postdoctoral Researcher Ohio State University (2000-2003)
Australian National University Ph.D. (1999)
University of Sydney B.Sc. (1991)
Research Interests – Reactive Intermediates and Photochemistry
Reactive Intermediates – as the name suggests, these are compounds that are formed and destroyed over the course of a chemical reaction, not only those encountered in synthetic chemistry, but also those of biological and environmental importance. Depending on their structure, these compounds may have lifetimes ranging from hours to billionths of a second. It turns out that despite (or perhaps because of) their ephemeral nature, the outcomes of many reactions are dependent on the structure and reactivity of the intermediates formed during the reaction. If we want to understand and control chemical reactivity, then understanding the nature of reactive intermediates is an important step in doing so.
Studying reactive intermediates requires a number of different approaches – a single type of experiment often cannot yield all the data we need. We, in conjunction with our collaborators at other institutions, employ a diverse range of experimental techniques; from standard analytical methods (UV, NMR, LC and GC), to more specialized techniques such as laser flash photolysis (LFP), mass spectrometry, and matrix-isolated infra-red, UV and EPR spectroscopy. Often, we use computational chemistry to provide support and insight into our experimental observations. Synthesis of reactive intermediate precursors, which may be decomposed thermally, or by interaction with light (photochemistry), also plays a significant role.
Most stable organic chemicals contain carbon and nitrogen/oxygen atoms which have eight electrons associated with them (a filled valence shell, or octet). We are interested in systems where carbon or oxygen have only seven such electrons (free radicals); radicals such as hydroxyl (HO•), alkoxyl (RO•) and peroxyl (ROO•) are important members of a general group known as reactive oxygen species (ROS). These species are known to play pivotal roles in a number of diverse areas of biological and environmental importance. The processes range from cellular responses of organisms to oxidative stress, to oxidative removal of volatile organic compounds from the atmosphere, to advanced oxidation methods in water treatment systems. We are interested in developing analytical methods that can be used to probe the reactions of these molecules; their reactivity, their selectivity, and their dependence on environmental factors such as solvent and interface effects. The obtained insight will be of benefit to these fields.
Other systems of interest to us are those where nitrogen atoms formally have only six valence electrons (nitrenes). This is typically not a tenable situation to be in, and so these species tend to be highly reactive, and in many (but not all) cases their high reactivity can lead to poor selectivity in the products they generate. If one wishes to harness the high reactivity synthetically without the selectivity headaches, then we need a good understanding, and reliable models for, the reactivity of these species, and we use a range of methods to probe these compounds and elucidate their reactions.
- Poole, J.S. “Recent Advances in the Photochemistry of Heterocyclic N-Oxides and their Derivatives” Top. Heterocyc. Chem., 2017, O. Larionov Ed., Springer-Nature, 111-151.
- Ribblett, A.; Poole, J.S.* “A Laser Flash Photolysis Study of Azo-Compound Formation from Aryl Nitrenes at Room Temperature” J. Phys. Chem. A, 2016, 120, 4267-4276.
- Koirala, D.; Poole, J. S.; Wenthold, P. G*.; “Reactivity of 3- and 4-Pyridinylnitrene N-oxide radical anions”, Int. J. Mass Spectrom., 2015, 378, 69-75.
- Modglin, J.D.; Erdely, V; Lin, C-Y; Coote, M.L.; Poole, J.S.* “Hammett Correlations in the Chemistry of 3-Phenylpropyl Radicals", J. Phys. Chem. A., 2011, 115, 14687-96.
- Sallans, L.; Poole, J.S.* “On the Photochemistry of 4-Azidoquinoline 1-Oxide: Structural Elucidation of Primary Photoproduct”, J. Mol. Struct., 2011, 1003, 41-46.
- Modglin, J.D.; Dunham, J.C.; Gibson, C.W.; Lin, C-Y.; Coote, M.L.; Poole, J.S.* “Computational Study of the Chemistry of 3-Phenylpropyl Radicals”, J. Phys. Chem. A, 2011, 115, 2431-2441
- Poole, J.S.* “A Computational Study of the Chemistry of Substituted 3-Nitrenopyridine 1-Oxides”, J. Mol. Struct.:THEOCHEM, 2009, 894, 93-102.
- Crabtree, K.N.; Hostetler, K.J.; Munsch, T.E.; Neuhaus, P.; Lahti, P.L.; Sander, W.; Poole, J.S.* “Comparative Study of the Photochemistry of the Azidopyridine 1 Oxides”, J. Org. Chem., 2008, 73, 3441-3451.
- Hostetler, K.J.; Crabtree, K.N.; Poole, J.S.* “The Photochemistry of 4-Azidopyridine-1-Oxide”, J. Org. Chem., 2006, 71, 9023-9029.
- Hostetler, K.J.; Poole, J.S.; Fanwick, P.E.* “N'-[5'-(3',5'-dimethoxycarbonyl-2'-pyrazolinyl)]methyl-4-aminopyridine-1-oxide monohydrate” Acta Cryst., Sect. E., 2006, E62, o3015-3016.
- Yonekawa, S.; Goodpaster, A.M.; Abel, B.A.; Paulin, R.G.; Sexton, C.W.; Poole, J.S.; Storhoff, B.N.*; Fanwick, P.E. “Synthesis, Properties and X-ray Structure of 5-Azido-2-methoxy-1,3-xylyl-18-crown-5”, J. Heterocyclic Chem., 2006, 43, 689-694
- DeMatteo, M; Poole, J S; Shi, X; Sachdeva, R; Hatcher, P G; Hadad, C M;* Platz, M S;* “On the Electrophilicity of Hydroxyl Radical: A Laser Flash Photolysis and Computational Study.” J. Am. Chem. Soc. 2005, 127, 7094-7109.
- Poole, J.S;* Shi, X; Hadad, C.M;* Platz, M.S;* “Reaction of Hydroxyl Radical with Aromatic Hydrocarbons in Non-Aqueous Solutions – a Laser Flash Photolysis Study in Acetonitrile.” J. Phys. Chem. A. 2005, 109, 2547-2551.
- Shi, X; Poole, J.S; Emineke, I; Burdzinski, G; Platz, M.S.* “Time Resolved Spectroscopy of the Excited Singlet States of Tirapazamine and Desoxytirapazamine.” J. Phys. Chem., A. 2005, 109, 1491-1496.