The structure, electronic properties, and chemical reactivity of pyrene and its three monochlorinated derivatives have been theoretically studied by using density functional theory (DFT). Several methods and basis sets are tested for the optimization of the geometrical structure and the B3LYP/6-311G** method/basis set is found to be the most suitable in predicting the heat of formation of pyrene and the minimum energy optimized structure of pyrene and its monochlorinated derivatives. The geometrical parameters and the heat of formation of pyrene are in good agreement with available experimental data. The chemical reactivity and stability of the four compounds are investigated. The computed results agree well with experimental results of monochlorination of the pyrene molecule. The relative stability of the monochlorinated pyrene compounds is in the order: 1-chloropyrene > 4-chloropyrene > 2-chloropyrene.
KeywordsDFTPyreneChloropyreneHeat of FormationChemical Reactivity
Pagnoni, A., Kligman, A.M. and Stoudenayer, T. (1998) Pyranine, a Fluorescent Dye, Detects Subclinical Injury to Sodium Lauryl Sulfate. Journal of Cosmetic Science, 49, 33-38.
Clar, E., Roberston, J.M., Schloegl, R. and Schmidt, W. (1981) Photoelectron Spectra of Polynuclear Aromatics. 6. Applications to Structural Elucidation: “Circumanthracene”. Journal of the American Chemical Society, 103, 1320-1328. http://dx.doi.org/10.1021/ja00396a003
Goodpaster, J.V., Harrison, J.F. and McGuffin, V.L. (1998) Ab Initio Study of Polycyclic Aromatic Hydrocarbons in Their Ground and Excited States. The Journal of Physical Chemistry A, 102, 3372-3381. http://dx.doi.org/10.1021/jp980467k
Kerr, C.E., Mitchell, C.D., Headrick, J., Eaton, B.E. and Netzel, T.L. (2000) Synthesis and Photophysics of a 1-Pyrenyl Substituted 2’-Deoxyuridine-5-carboxamide Nucleoside: Electron Transfer Products as CISINDO/S Excited States. The Journal of Physical Chemistry B, 104, 1637-1650. http://dx.doi.org/10.1021/jp992773j
Charles Li, X.-C., Okamura, Y., Ueno, K., Tashiro, M. and Prakash, G.K. (2005) Organic Electroluminescent Device Based on Pyrene Derivatives. US Patent No. 6852429.
Luthe, G.M., Ariese, F., Udo, A. and Brinkman, T. (2002) Monochlorinated Polycyclic Aromatic Hydrocarbons: Standards in Environmental Chemistry and Biochemical Applications. The Handbook of Environmental Chemistry, 3N, 249-275.
Dewhurst, F. and Kitchen, D.A. (1972) Synthesis and Properties of 6-Substituted Benzo[a]pyrene Derivatives. Journal of the Chemical Society, Perkin Transactions 1, 2,710-712.
Ohura, T., Kitazawa, A. and Amagai, T. (2004) Seasonal Variability of 1-Chloropyrene on Atmospheric Particles and Photostability in Toluene. Chemosphere, 57, 831-837. http://dx.doi.org/10.1016/j.chemosphere.2004.08.069
Muff, J. and Sogaard, E.G. (2011) Identification and Fate of Halogenated PAHs Formed during Electrochemical Treatment of Saline Aqueous Solutions. Journal of Hazardous Materials, 186, 1993-2000. http://dx.doi.org/10.1016/j.jhazmat.2010.12.110
Takeuchi, H. (2013) Structures, Stability, and Growth Sequence Patterns of Small Homoclusters of Naphthalene, Anthracene, Phenanthrene, Phenalene, Naphthacene, and Pyrene. Computational and Theoretical Chemistry, 1021, 84-90. http://dx.doi.org/10.1016/j.comptc.2013.06.029
Robertson, J.M. and White, J.G. (1947) The Crystal Structure of Pyrene. A Quantitative X-Ray Investigation. Journal of the Chemical Society, 1, 358-368. http://dx.doi.org/10.1039/jr9470000358
Jensen, A. and Berg, A. (1965) Reactions of Halopyrenes with Phenyllithium in Ether. Acta Chemica Scandinavica, 19, 1838-1842. http://dx.doi.org/10.3891/acta.chem.scand.19-1838
Hu, J., Jin, X., Kunikane, S., Terao, Y. and Aizawa, T. (2006) Transformation of Pyrene in Aqueous Chlorination in the Presence and Absence of Bromide Ion:? Kinetics, Products, and Their Aryl Hydrocarbon Receptor-Mediated Activities. Environmental Science Technology, 40, 487-493. http://dx.doi.org/10.1021/es0516108
Fabina, J. and Hartmann, H. (1980) Theoretical Treatment and Empirical Rules. Springer, Berlin, 117.
Vektariene, A, Vektaris, G. and Svoboda, J. (2009) A Theoretical Approach to the Nucleophilic Behavior of Benzofused Thieno[3,2-b]furans Using DFT and HF Based Reactivity Descriptors. ARKIVOC, 7, 311-329. http://dx.doi.org/10.3998/ark.5550190.0010.730
Parr, R.G. and Pearson, R.G. (1983) Absolute Hardness: Companion Parameter to Absolute Electronegativity. Journal of the American Chemical Society, 105, 7512. http://dx.doi.org/10.1021/ja00364a005
Li, Y.-F., Fan, X.-W., Wang, Z.-Y. and Ju, X.-H. (2009) A Density Functional Study of Substituted Pyrazole Derivatives. Journal of Molecular Structure: THEOCHEM, 896, 96-102. http://dx.doi.org/10.1016/j.theochem.2008.11.004
Smith, L., Bjellerup, L., Krook, S. and Westermark, H. (1953) Heats of Combustion of Organic Chloro Compounds Determined by the “Quartz Wool” Method. Acta Chemica Scandinavica, 7, 65-86. http://dx.doi.org/10.3891/acta.chem.scand.07-0065
Nilsson, U.L. and Ostman, C.E. (1983) Chlorinated Polycyclic Aromatic Hydrocarbons: Method of Analysis and Their Occurrence in Urban Air. Environmental Science Technology, 27, 1826-1831. http://dx.doi.org/10.1021/es00046a010
Roux, M.V., Temprado, M., Chickos, J.S. and Nagano, Y. (2008) Critically Evaluated Thermochemical Properties of Polycyclic Aromatic Hydrocarbons. Journal of Physical and Chemical Reference Data, 37, 1855-1996. http://dx.doi.org/10.1063/1.2955570