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FT-IR and FT Raman: Experimental and Theoretical Studies and HOMO-LUMO Analysis of 1,2,4,5-Tetracyanobenzene

Experimental and theoretical studies on molecular and vibrational structure of 1,2,4,5-Tetracyanobenzene (TCNB) have been undertaken in the present work. The FT-IR spectrum and FT Raman spectrum of TCNB were recorded respectively in the region 4000–400 cm−1 and 2500-400 cm-1. The optimized geometries in the ground state were calculated by DFT (B3LYP) methods with 6-311G basis set. The optimized structural shown the difference in the bond lengths and some angles are very little affected with a small reduction. The computational results indicate that the molecule adopts a plane geometry and belongs to the D2h point group with the aromatic ring lying in the plane of symmetry. The molecular electrostatic potential shown that the two protons of TCNB as well as the benzene ring are in electron deficient region whereas the CN group are in electron rich region. The carbon atom of CN group and the carbon on the benzene ring are in antibonding interactions in HOMO and in bonding interactions in the LUMO. The harmonic vibrational frequencies, infrared intensities and Raman activities of the TCNB were evaluated. After scaling, the computational wavenumbers are in agreement with the experimental values. A detailed interpretation of the infrared and Raman spectra of TCNB is presented.

Tetra-Cyanobenzene, DFT Calculations, Symmetry, IR and Raman

Ali Sanda Bawa, Abdoul-Rachid Chaibou Yacouba, Seydou Ouedraogo, Mabinty-Bayo Bangoura, Karifa Bayo, et al. (2023). FT-IR and FT Raman: Experimental and Theoretical Studies and HOMO-LUMO Analysis of 1,2,4,5-Tetracyanobenzene. Science Journal of Chemistry, 11(4), 161-167.

Copyright © 2023 Authors retain the copyright of this article.
This article is an open access article distributed under the Creative Commons Attribution License ( which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

1. Ali Sanda Bawa, Rita Meunier-Prest, Yoann Rousselin, Jean-Pierre Couvercelle, Christine Stern, Bernard Malézieux and Marcel Bouvet; Series of charge transfer complexes obtained as crystals in a confined environment; Cryst Eng Comm, 2021, 23, 6418–6426.: 10.1039/D1CE00929J.
2. Micheal Huth, Organic Charge Transfert Systems: The next step in Molecular Electronics, Beilstein Bozen on Molecular Engineering and Control, Prien (Chiemsee), Germany 2012.
3. J. Fünfschilling, M. Samoc, D. F. Wiliams, Quenching of the delayed fluorescence by charge carriers in crystals of anthracene-TCNB CT complex; Chem. Phys. Lett. 96 (1983) 157-160.
4. T. Kobayashi, S. Nagakura, Two-photon excitation inorganic crystals by dye laser; Chem. Phys. Lett. 13 (1972) 217.
5. G. Agostini, C. Coravaja, G. Giacometti, L. Pasimeni, D. A. Clemente, Photoexcited triplets and structural properties of single crystals of the trans-stilbene-1,2,4,5-tetracyanobenzene (1: 2) complex, J. Phys. Chem. 92 (1988) 997. DOI: 10.1021/j100315a028.
6. H. Jiang, P. Hu, J. Ye, K. K. Zhang, Y. Long, W. Hu and C. kloc, J. Mater. Chem. C, 2018, 1884-1902.
7. X. Ye, Y. Liu, Q. Guo, Q. Han, C Ge; S Cui, L Zhang and X. Tao, Nat. Commun., 2019, 10, 1-9.
8. J. Umemura and T. Takenaka, Cartesian Displacements of Normal Vibrations of 1,2,4,5-Tetracyanobenzene and 1,2,4,5-Tetracyanobenzene-d2 Molecules, Bull. Inst. Chem. Res., Kyoto Univ., 51, 206 (1973).
9. Tohru TAKENAKA, Junzo UMEMURA, Shinichi TADOKORO, Shinzaburo OKA and Takashi KOBAYASH; Vibrational Spectra of 1,2,4,5-Tetracyanobenzene and 1,2,4,5-Tetracyanobenzen-d2Crystals; Bull. Inst. Chem. Res., Kyoto Univ., Vol. 56, No. 4, 1978.
10. Schultz, G., Szabados, Á., Tarczay, G. et al. Molecular Structure of 1,2,4,5-Tetracyanobenzene from Gas-Phase Electron Diffraction and Theoretical Calculations. Structural Chemistry 10, 149–155 (1999).
11. S. Chakraborty, S. Wategaonkar, Spectroscopic characterization of 1,2,4,5-tetracyanobenzene, Chemical Physics Letters 460 (2008) 18–22.
12. M. J. Frisch, G. W. Trucks, H. B. Schlegel et al., “Gaussian 09, R. A gaussian. Inc., Wallingford CT,” vol. 121, pp. 150–166, 2009. 10.1016/j.cplett.2008.05.037.
13. P. B. Nagabalasubramanian, S. Periandym; FT IR and FT Raman, molecular geometry, vibrational assignments, ab initio and density functional theory calculations for 1, 5-methylnaphthalene; Spectrochimica Acta Part A 77 (2010) 1099–1107.
14. E. D. Glendening, A. E. Reed, J. E. Carpenter, F. Weinhold, and N. B. O. Version, 3.1 Program Manual, University of Wisconsin, Madison, 1998.
15. J. Foresman and E. Frish, Exploring Chemistry with Electronic Structure Methods, Gaussian Inc., Pittsburg, USA, 1996.
16. I Fleming, Frontier Orbitals and Organic Chemical Reactions, John Wiley and Sons, NewYork, 05–27, (1976).
17. Wilson E B, Decius J C & Cross P C, Molecular vibration: the theory of infrared and Raman vibrational spectra, Dover Publ Inc New York, 1980. urn: lcp: molecularvibrati00wils: lcpdf: e3fe33b0-1929-46a2-920c-91471ef13761.
18. T. Prabhu, S. Periandy, S. Mohan, Spectroscopic (FT IR and FT Raman) analysis and vibrational study on 2, 3-dimethylnaphthalene using ab-initio HF and DFT calculations, Spectrochimica Acta Part A 78 (2011) 566–574.
19. V. Krishnakumar, N. Prabavathi, S. Muthunatesan, Density functional theory study of vibrational spectra, and assignment of fundamental vibrational modes of 1-bromo-4-fluoronaphthalene, Spectrochimica Acta Part A 70 (2008) 991–996.
20. G. Keresztury, Raman spectroscopy: theory, in: J. M. Chalmers, P. R. Griffiths (Eds.), Handbook of Vibrational Spectroscopy, vol. 1, John Wiley & Sons Ltd., 2002, p.71. PrintISBN: 9783527297825| Online ISBN: 9783527602308 |DOI: 10.1002/3527602305.
21. L. Goodman, A. G. Ozkabak, S. N. Thakur, Abenchmark vibrational potential surface: ground-state benzene, J. Phys. Chem. 95 (1991) 9044–9058.
22. The official web site of National Institute of Advanced Industrial Science and Technology (AIST), Research Information Database (RIO-DB).
23. S. George, Infrared and Raman Characteristic Group Frequencies—Tables and Charts, thirded., (Wiley, New York, 2001).
24. V. Krishnakumar, N. Surumbarkuzhali, S. Muthunatesan, Scaled quantum chemical studies on the vibrational spectra of 4-bromobenzonitrile, Spectrochimica Acta Part A 71 (2009) 1810–1813.
25. M Alcolea Palafox and V K Rastogi, Spectra and structure of benzonitriles and some of its simple derivatives, Asian Journal of Physics Vol. 22, No 3 (2013) 1-30.
26. N. Sundaraganesan, G Elango, S Sebastian and P Subramani, Molecular structure; vibrational spectroscopic studies and analysis of 2-fluoro-5-methylbenzonitrile, Indian J PURE & APPL PHYS, Vol 47, July 2009.