Solvatochromism and Molecular Selectivity of C-(4-chlorophenyl)-N-phenylnitrone: A Photophysical Study

Abstract

The ground state interaction of C-(4-chlorophenyl)-N-phenylnitrone (N1) with three different α, β-unsaturated ketones (K1 - K3) in very dilute solution (10-6 mol dm-3) has been noticed through charge transfer band formation in the visible region. The experimentally measured transition dipole, ground state resonance energy and formation constants of the complexes indicate interaction selectivity of the acyclic nitrone (N1) for the ketones. Molar absorptivity of the absorbing complexes were determined for all the three N1/K (1:1) interacting systems in toluene. Experimental findings were well rationalized with the help of electron density based global electrophilicity and nucleophilicity indices as well as with frontier molecular orbital calculations.

Share and Cite:

S. Salampuria, T. Chaudhuri and M. Banerjee, "Solvatochromism and Molecular Selectivity of C-(4-chlorophenyl)-N-phenylnitrone: A Photophysical Study," Optics and Photonics Journal, Vol. 2 No. 1, 2012, pp. 30-39. doi: 10.4236/opj.2012.21005.

Conflicts of Interest

The authors declare no conflicts of interest.

References

[1] L. J. Prins, D. N. Reinhoudt and P. Timmerman, “Non- covalent Synthesis Using Hydrogen Bonding,” Ange- wandte Chemie International Edition, Vol. 40, No. 13, 2001, pp. 2382-2426. doi:10.1002/1521-3773(20010702)40:13<2382::AID-ANIE2382>3.0.CO;2-G
[2] S. Bhattacharya, M. Banerjee and A. K. Mukherjee, “Study of the Formation Equilibria of Electron Donor- Acceptor Complexes between [60]-Fullerene and Methyl- benzenes by Absorption Spectrometric Method,” Spec- trochimica Acta Part A, Vol. 57, No. 7, 2001, pp. 1463- 1470. doi:10.1016/S1386-1425(00)00489-3
[3] S. Bhattacharya, S. Bhattacharya (Banerjee), K. Ghosh, S. Basu and Manas Banerjee, “Study of Electron Donor- Acceptor Complex Formation of o-ChloranilWith a Se- ries of Phosphine Oxides and Tri-n-butyl Phosphate by the Absorption Spectrometric Method,” Journal of Solu- tion Chemistry, Vol. 35, No. 4, 2006, pp. 519-539. doi:10.1007/s10953-005-9013-x
[4] S. Bhattacharya, S. K. Nayak, S. K. Chattopadhyay, M. Banerjee a nd A. K. Mukherjee, “Absorption Spectroscopic Study of EDA Complexes of [70]Fullerene with a series of Methyl Benzenes,” Spectrochimica Acta Part A, Vol. 57, No. 2, 2001, pp. 309-313. doi:10.1016/S1386-1425(00)00388-7
[5] Z. Zou, J. Ye and H. Arakawa, “Role of R in Bi2RNbO7 (R = Y, Rare Earth): Effect on Band Structure and Photo- catalytic Properties,” Journal of Physical Chemistry B, Vol. 106, No. 3, 2002, pp. 517-520. doi:10.1021/jp012982f
[6] A. Eychmuller and A. L. Rogach, “Chemistry and Pho- tophysics of Thiol-Stabilized II-VI Semiconductor Nano- crystals,” Pure and Applied Chemistry, Vol. 72, No. 1-2, 2000, pp. 179-188. doi:10.1351/pac200072010179
[7] T. H. Ghaddar, J. K. Whitesell and M. A. Fox, “Excimer Formation in a Naphthalene-Labeled Dendrimer,” Jour- nal of Physical Chemistry B, Vol. 105, No. 37, 2001, pp. 8729-8731. doi:10.1021/jp010933x
[8] A. S. Baranski and W. R. Fawcett, “Solvent Effects in Sim- ple Electron Transfer Reactions,” Winkler, K. Ed., Journal of the Chemical Society, Faraday Transactions, Vol. 92, 1996 pp. 3899-3904.
[9] M. Ricco, M. Bisbiglia, R. Derenzi and F. Bolzoni, “Ob- servation of Superconductivity in TDAEC60,” Solid State Communications, Vol. 101, No. 6, 1997, pp. 413-416.
[10] S. M. Andrade, S. M. B. Costa and R. Pansu, “Structural Changes in w/o TritonX-100/Cyclohexane-Hexanol/Water Microemulsions Probed by a Fluorescent Drug Piroxi- cam,” Journal of Colloid and Interface Science, Vol. 226, No. 2, 2000, pp. 260-268. doi:10.1006/jcis.2000.6821
[11] A. Polozova and B. J. Litman, “Cholesterol-Dependent Recruitment of di22:6-PC by a G Protein-Coupled Re- ceptor into Lateral domains,” Journal of Biophysics, Vol. 79, No. 5, 2000, pp. 2632-2643. doi:10.1016/S0006-3495(00)76502-7
[12] C. Reichardt, “Solvatochromic Dyes as Solvent Polarity Indicators,” Chemical Reviews, Vol. 94, No. 4, 1994, pp. 2319-2358. doi:10.1021/cr00032a005
[13] A. Padwa and W. H. Pearson, “Synthetic Applications of 1,3-Dipolar Cycloaddition Chemistry towards Heterocy- cles and Natural Products,” John Wiley & Sons, New York, 2002. doi:10.1002/0471221902
[14] A. Banerji and P. Sengupta, “Recent Studies on 1,3-Dipolar Cycloadditions of Nitrones,” Journal of Indian Institute of Science, Vol. 81, No. 3, 2001, pp. 313-323.
[15] A. K. Parhi and R.W. Franck, “A Weinreb Nitrile Oxide and Nitrone for Cycloaddition,” Organic Letters, Vol. 6, No. 18, 2004, pp. 3063-3065. doi:10.1021/ol0489752
[16] Y. Zeng, B. T. Smith, J. Hershberger and J. Aube′, “Re- arrangements of Bicyclic Nitrones to Lactams: Compari- son of Photochemical and Modified Barton Conditions,” Journal of Organic Chemistry, Vol. 68, No. 21, 2003, pp. 8065-8067. doi:10.1021/jo035004b
[17] K. B. Jensen, M. Roberson and K. A. Jorgensen, “Cata- lytic Enantioselective 1,3-Dipolar Cycloaddition Reac- tions of Cyclic Nitrones: A Simple Approach for the Formation of Optically Active Isoquinoline Derivatives,” Journal of Organic Chemistry, Vol. 65, No. 26, 2000, pp. 9080-9084. doi:10.1021/jo001157c
[18] K. B. G. Torssell, “Nitrile Oxides, Nitrones and Nitro- nates in Organic Synthesis,” VCH, Weinheim, 1988.
[19] E. Breuer, “Nitrones and Nitronic Acid Derivatives: Their Structures and Their Roles in Synthesis,” In: S. Patai, Ed., The Chemistry of Amino, Nitroso and Nitro Compounds and Their Derivatives, John Wiley & Sons, New York, 1982.
[20] A. Banerji, D. Bandyopadhyay, T. Prangé and A. Neuman, “Unexpected Cycloadducts from 1,3-Dipolar Cycloaddi- tion of 3,4-Dehydromorpholine N-Oxide to N-Cinnamoyl Piperidines—First Report of the Novel Formation of 2:1 Cycloadducts,” Tetrahedron Letters, Vol. 46, No. 15, 2005, pp. 2619-2622. doi:10.1016/j.tetlet.2005.02.083
[21] R. Huisgen, “1,3-Dipolar Cycloaddition Chemistry,” In: A. Padwa, Ed., Wiley, New York, 1984.
[22] K. V. Gothlf and K. A. Jorgensen, “Asymmetric 1,3-Di- polar Cycloaddition Reactions,” Chemical Review, Vol. 98, No. 2, 1998, pp. 863-909. doi:10.1021/cr970324e
[23] L. R. Domingo, E. Chamorro and P. Pérez, “Understand- ing the Reactivity of Captodative Ethylenes in Polar Cy- cloaddition Reactions. A Theoretical Study,” Journal of Organic Chemistry, Vol. 73, No. 12, 2008, pp. 4615-4624. doi:10.1021/jo800572a
[24] T. K. Das, S. Salampuria and M. Banerjee, “Computa- tional DFT Study of the 1,3-dipolar Cycloadditions of 1- Phenylethyl-trans-2-methyl Nitrone to Styrene and 1-Pheny- lethyl Nitrone to Allyl Alcohol,” Journal of Molecular Structure: THEOCHEM, Vol. 959, No. 1-3, 2010, pp. 22- 29. doi:10.1016/j.theochem.2010.08.001
[25] H. A. Benesi and J. H. Hildebrand, “A Spectrophotomet- ric Investigation of the Interaction of Iodine with Aro- matic Hydrocarbons,” Journal of American Chemical So- ciety, Vol. 71, No. 8, 1949, pp. 2703-2707. doi:10.1021/ja01176a030
[26] K. A. Connors, “Binding Constants: The Measurement of Molecular Complex Stabilility,” John Wiley & Sons, New York, 1987.
[27] T. Chaudhuri, D. Goswami, M. Banerjee, S. Chatto- padhyay and S. K. Nayak, “Supramolecular Selectivity of [60]-Fullerene among Equivalently Photoactive Porphy- rins,” Journal of Luminescence, Vol. 130, No. 10, 2010, pp. 1750-1755. doi:10.1016/j.jlumin.2010.04.004
[28] R. G. Parr, L. V. Szentpaly and S. Liu, “Electrophilicity Index,” Journal of American Chemical Society, Vol. 121, No. 9, 1999, pp. 1922-1924. doi:10.1021/ja983494x
[29] A. Corsaro, V. Pistara, A. Rescifina, A. Piperno, M. Chiacchio and G. Romeo, “A DFT Rationalization for the Observed Regiochemistry in the Nitrile Oxide Cyclo- addition with Anthracene and Acridine,” Tetrahedron, Vol. 60, No. 31, 2004, pp. 6443-6451. doi:10.1016/j.tet.2004.06.052
[30] R. Contreras, J. Andres, V. S. Safont, P. Campodonico and J. G. Santos, “A Theoretical Study on the Relationship between Nucleophilicity and Ionization Potentials in Solution Phase,” Journal of Physical Chemistry A, Vol. 107, No. 29, 2003, pp. 5588-5593. doi:10.1021/jp0302865
[31] J. P. Freeman, “Organic Synthesis, Collective Volume 1,” R. L. Danheiser, (Ed.), 1941, p. 78. Volume 2, 1922, p. 1.
[32] A. Frisch, M. J. Frisch, F. R. Clemente and G. W. Trucks, “Gaussian 09 Cluster/LAN Parallel Version with Linda,” Gaussian Inc., Wallingford, 2009.
[33] V. Gutmann, “The Donor-Aceeptor Approach to Mole- cular Interactions,” Plenum Press, New York, 1978. doi:10.1007/978-1-4615-8825-2
[34] F. L. Riddle Jr. and F. M. Fowkes, “Spectral Shifts in Acid-Base Chemistry. 1. Van der Waals Contributions to Acceptor Numbers,” Journal of American Chemical So- ciety, Vol. 112, No. 9, 1990, pp. 3259-3264. doi:10.1021/ja00165a001
[35] M. J. Kamlet and R. W. Taft, “The Solvatochromic Com- parison Method. I. The Beta-Scale of Solvent Hydrogen- Bond Acceptor (HBA) Basicities,” Journal of American Chemical Society, Vol. 98, No. 2, 1976 pp. 377-383. doi:10.1021/ja00418a009
[36] T. Chaudhuri, S. Mula, S. Chattopadhyay and M. Baner- jee, “Photophysical Properties of the 8-Phenyl Analogue of PM567: A Theoretical Rationalization,” Spectro- chimica Acta Part A, Vol. 75, No. 2, 2010, pp. 739-744. doi:10.1016/j.saa.2009.11.048
[37] T. Chaudhuri, P. Shukla, S. K. Nayak, S. Chattopadhyay and M. Banerjee, “Solvent Effect on Photophysical Prop- erties and Mg2+ Binding of 1,3-Diphenyl-propane-1,3- dione,” Journal of Photochemistry and Photobiology A: Chemistry, Vol. 215, No. 1, 2010, pp. 31-37. doi:10.1016/j.jphotochem.2010.07.017
[38] I. R. Gould, D. Noukakis, L. Gomez-Jahn, R. H. Young, J. Goodman and S. Farid, “Radiative and Nonradiative Elec- tron Transfer in Contact Radical-Ion Pairs,” Chemical Physics, Vol. 176, No. 2-3, 1993, pp. 439-456. doi:10.1016/0301-0104(93)80253-6
[39] G. Briegleb and J. Czekalla, “Intensity of Electron Tran- sition Bands in Electron Donator-Acceptor Complexes,” Zeitschrift für physikalische Chemie (Frankfurt), Vol. 24, 1960, pp. 37-54.
[40] P. Jaramillo, L. R. Domingo, E. Chamorro and P. Pérez, “A Further Exploration of a Nucleophilicity Index Based on the Gas-Phase Ionization Potentials,” Journal of Mo- lecular Structure: THEOCHEM, Vol. 865, No. 1-3, 2008, pp. 68-72. doi:10.1016/j.theochem.2008.06.022
[41] L. R. Domingo, M. J. Aurell, P. Pe′rez and R. Contreras, “Quantitative Characterization of the Global Electrophi- licity Power of Common Diene/Dienophile Pairs in Diels- Alder Reactions,” Tetrahedron, Vol. 58, No. 22, 2002, pp. 4417-4423. doi:10.1016/S0040-4020(02)00410-6
[42] N. Acharjee, A. Banerji and T. Prange, “DFT Study of 1,3-Dipolar Cycloadditions of C,N-Disubstituted Aldoni- trones to Chalcones Evidenced by NMR and X-Ray Ana- lysis,” Monatshefte für Chemie, Vol. 141, No. 11, 2010, pp. 1213-1221. doi:10.1007/s00706-010-0393-2

Copyright © 2024 by authors and Scientific Research Publishing Inc.

Creative Commons License

This work and the related PDF file are licensed under a Creative Commons Attribution 4.0 International License.