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Vol. 26 No. 20 (2014)

Copyright (c) 2014 Saied M. Soliman1, Ahmed A. Badr2

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This work is licensed under a Creative Commons Attribution 4.0 International License.

DFT Studies on the Molecular Structure, Electronic and Spectroscopic Properties of Free and Zinc(II) Coordinated N-Alkyl Thiourea Ligands

https://doi.org/10.14233/ajchem.2014.17462
Saied M. Soliman1
1Department of Chemistry, Rabigh College of Science and Art, King Abdulaziz University, Rabigh, Saudi Arabia 2Department of Chemistry, Faculty of Science, Alexandria University, P.O. Box 426 Ibrahimia, 21525 Alexandria, Egypt *Corresponding authors: Tel.: +966 565450752; E-mail: saied1soliman@yahoo.com
Ahmed A. Badr2
1Department of Chemistry, Rabigh College of Science and Art, King Abdulaziz University, Rabigh, Saudi Arabia 2Department of Chemistry, Faculty of Science, Alexandria University, P.O. Box 426 Ibrahimia, 21525 Alexandria, Egypt *Corresponding authors: Tel.: +966 565450752; E-mail: saied1soliman@yahoo.com

Corresponding Author(s) : Saied M. Soliman1

Asian Journal of Chemistry, Vol. 26 No. 20 (2014)

Abstract

The molecular structure, vibrational spectra and non linear optical properties of five thiourea ligands (L) and their zinc chloride complexes; [ZnL2Cl2] are calculated using DFT/B3LYP method. The results of calculations showed an increase of the C-N double bond characters and decrease of the C-S bond order due to the coordination between Zn2+ and thiourea ligands through the S-atom. A low frequency shift for the n(C-S) bands and high frequency shift for n(C-N) bands are predicted in case of the zinc(II) complexes compared to the free ligands. Also, red shifts for the n(N-H) stretches involved in the formation of intramolecular NH---Cl H-bonds while the rest of the n(N-H) modes undergo blue shifts. High polar character of the C-N and C-S bonds is predicted. Molecular electrostatic potential predicted the higher reactivity of the S-site of the thiourea ligands towards electrophilic attack compared to the N-sites.

Keywords

Thiourea DFT Vibrational spectra Intramolecular H-bond Non-linear optical.
M. Soliman1, S., & A. Badr2, A. (2014). DFT Studies on the Molecular Structure, Electronic and Spectroscopic Properties of Free and Zinc(II) Coordinated N-Alkyl Thiourea Ligands. Asian Journal of Chemistry, 26(20), 6926–6930. https://doi.org/10.14233/ajchem.2014.17462
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References
  1. W. Zhou, L. Zhu, Y. Zhang, Z. Yu, L. Lu and X. Yang, Vib. Spect., 36, 73 (2004).
  2. M.J. Moloto, M.A. Malik, P.O 'Brien, M. Motevalli and G.A. Kolawole, Polyhedron, 22, 595 (2003).
  3. M.R. Malik, V. Vasylyeva, K. Merz, N. Metzler-Nolte, M. Saleem, S. Ali, A.A. Isab, K.S. Munawar and S. Ahmad, Inorg. Chim. Acta, 376, 207 (2011).
  4. Y. Omote, R. Kobayashi, C. Kashima and N. Sugiyama, Bull. Chem. Soc. Jpn., 44, 3463 (1971).
  5. B.S. Garg and L. Kapur, Inorg. Chim. Acta, 170, 177 (1990).
  6. G.M.S. El-Bahy, B.A. El-Sayed and A.A. Shabana, Vib. Spect., 31, 101 (2003).
  7. M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman, J.A. Montgomery Jr., T. Vreven, K.N. Kudin, J.C. Burant, J.M. Millam, S.S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G.A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J.E. Knox, H.P. Hratchian, J.B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R.E. Stratmann, O. Yazyev, A.J. Austin, R. Cammi, C. Pomelli, J.W. Ochterski, P.Y. Ayala, K. Morokuma, G.A. Voth, P. Salvador, J.J. Dannenberg, V.G. Zakrzewski, S. Dapprich, A.D. Daniels, M.C. Strain, O. Farkas, D.K. Malick, A.D. Rabuck, K. Raghavachari, J.B. Foresman, J.V. Ortiz, Q. Cui, A.G. Baboul, S. Clifford, J. Cioslowski, B.B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R.L. Martin, D.J. Fox, T. Keith, M.A. Al-Laham, C.Y. Peng, A. Nanayakkara, M. Challacombe, P.M.W. Gill, B. Johnson, W. Chen, M.W. Wong, C. Gonzalez and J. A. Pople, Gaussian-03, Revision C.01, Gaussian, Inc., Wallingford, CT (2004).
  8. http://www.ccdc.cam.ac.uk/data_request/cif.
  9. A.D. Burrows, R.W. Harrington and M.F. Mahon, Acta Crystallogr., 60E, m1317 (2004).
  10. R. Dennington II, T. Keith and J. Millam, GaussView, Version 4.1, Semichem Inc., Shawnee Mission, KS (2007).
  11. Y. Mido, H. Okada, N. Fujita, I. Kitagawa, T. Kitahata, M. Hashimoto, H. Yoshida and H. Matsuura, J. Mol. Struct., 415, 215 (1997).
  12. M.P. Andersson and P. Uvdal, J. Phys. Chem., 109, 2937 (2005).
  13. A. Destexhe, J. Smets, L. Adamowicz and G. Maes, J. Phys. Chem., 98, 1506 (1994).
  14. Y. Dimitrova and L.I. Daskalova, Spectrochim. Acta A, 71, 1720 (2009).
  15. M. Belletete, J.F. Morin, M. Leclerc and G. Durocher, J. Phys. Chem. A, 109, 6953 (2005).
  16. D. Zhenming, S. Heping, L. Yufang, L. Diansheng and L. Bo, Spectrochim. Acta A, 78, 1143 (2011).
  17. D. Sajan, H. Joe, V.S. Jayakumar and J. Zaleski, J. Mol. Struct., 785, 43 (2006).
  18. K.S.Thanthiriwatte and K.M. Nalin de Silva, J. Mol. Struct. THEOCHEM, 617, 169 (2002).
  19. R.G. Pearson, Proc. Natl. Acad. Sci. USA, 83, 8440 (1986).
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