DFT studies of all fluorothiophenes and their radical cations as candidate monomers for conductive polymers
محورهای موضوعی : Journal of the Iranian Chemical Research
Saeed Jameh-Bozorghi
1
,
Hossein Shirani
2
1 - Department of Chemistry, Islamic Azad University, Toyserkan Branch, Toyserkan, Iran
2 - Young Research Club, Islamic Azad University, Toyserkan Branch, Toyserkan, Iran
کلید واژه: DFT-B3LYP, Dipole moment, Fluorothiophenes, Conductive polymers,
چکیده مقاله :
In this paper, electronic, structural, and spectroscopic properties of mono-, di-, tri-, andtetrafluorothiophenes and their radical cations are studied using the density functional theory andB3LYP method with 6-311++G** basis set. Also the effects of the number and position of thesubstituent on the electrochemical properties of the thiophene ring have been studied usingoptimized structures obtained for these molecules and their cations, vibrational frequencies andnuclear chemical shielding constants of these compounds have been calculated and analyzed.The results of this study including charge and spin-density distribution, size and direction of thedipole moment vector, ionization potential, electric polarizability and NICS show that among allof these compounds 3-fluorothiophene as candidate monomer for new conductive polymers,possesses the most suitable conditions for electropolymerization.
[1] A.J. Heeger, J. Phys. Chem. B. 105 (2001) 8475-8483.
[2] A.G. MacDiarmid. Angew. Chem. Int. E. 40 (2001) 2581-2589.
[3] N. Hall. Chem. Commun. 1 (2003) 803-811.
[4] S. Neves, W.A. Gazotti, M.A. De Paoli, In Encyclopedia of Nanoscience and Nanotechnology, Vol. 2,
H.S. Nalwa (Ed.), American Scientific Publishers, Los Angeles (2004).
[5] R. Gangopadhyay. In Encyclopedia of Nanoscience and Nanotechnology, Vol. 2, H. S. Nalwa (Ed.),
pp. 105–131, American Scientific Publishers, Los Angeles (2004).
[6] G.G. Wallace, P.C. Innis, L.A.P. Kane-Maguire, In Encyclopedia of Nanoscience and
Nanotechnology, Vol. 4, H.S. Nalwa (Ed.), pp. 113–130, American Scientific Publishers, Los
Angeles (2004).
[7] A.J. Epstein, In Organic Electronic Materials: Conjugated Polymers and Low Molecular Weight
Organic Solids, Vol. 41, R. Farchioni and G. Grosso (Eds.), p. 3, Springer, Amsterdam (2001).
[8] X. Zhang and S. K. Manohar. Chem. Commun., 20 (2004) 2360-2369.
[9] L. Yu, J. I. Lee, K.W. Shin, C.E. Park, R. Holze. J. Appl. Polym. Sci. 88 (2003) 1550-1560.
[10] J.C. Michaelson, A.J. McEvoy, Chem. Commun. 79 (1994) 451-459.
[11] G.C. Li, Z.K. Zhang, Macromolecules 37 (2004) 2683-2692.
[12] L.M. Huang, Z.B. Wang, H.T. Wang, X.L. Cheng, A. Mitra, Y.X. Yan. J. Mater. Chem. 12 (2002)
388-399.
[13] J.M. Liu, S.C. Yang, Chem. Commun. 34 (1991) 1529-1538.
[14] X. Zhang, W.J. Goux, S.K. Manohar, J. Am. Chem. Soc. 126 (2004) 4502-4509.
L1
L2
L3
L4
L5
L6
Lumo
Homo
H. Shirani & S. Jameh-Bozorghi / J. Iran. Chem. Res. 3 (2010) 17-30
30
[15] W.G. Li, H.L. Wang, J. Am. Chem. Soc. 126 (2004) 2278-2284.
[16] H.J. Qiu, M.X. Wan, B. Matthews, L.M. Dai, Macromolecules 34 (2001) 675-681.
[17] Z.X. Wei, M.X. Wan, J. Appl. Polym. Sci. 87 (2003) 1297-1305.
[18] Z.X. Wei, Z.M. Zhang, M.X. Wan, Langmuir 18 (2002) 917-924.
[19] M.X. Wan, In Encyclopedia of Nanoscience and Nanotechnology, Vol. 2, H.S. Nalwa (Ed.), pp.
153–169, American Scientific Publishers, Los Angeles (2004).
[20] H.J. Qiu, M.X. Wan, J. Polym. Sci. Part A: Polym. Chem. 39 (2001) 3485-3493.
[21] M. S. Ram, S. Palaniappan, J. Molecular Catalysis A: Chemical. 201 (2003) 289-295.
[22] G.G. Wallace, G.M. Spinks, L.A.P. Kane-Maguire, P.R. Teasda, Conductive Electroactive Polymers:
Intelligent Polymer Systems, CRC Press, Queensland, (2009).
[23] F. Beck, U. Barsch, Makromol. Chem. 194 (1993) 2725-2732.
[24] R. Turcu, O. Pana, I. Bratu, M. Bogdon, J. Mol. Elect. 6 (1990) 1-12.
[25] C.A. Cutler, A.K. Burrell, D.L. Officer, C.O. Too, G.G. Wallace, Synth. Met. 128 (2002) 35-45.
[26] C.A. Cutler, A.K. Burrell, G.E. Collis, P.C. Dastoor, D.L. Officer, C.O. Too, G.G. Wallace, Synth.
Met. 123 (2001) 225-234.
[27] T.F. Oterom, E.L. Azelain, Polym. Comm. 29 (1988) 21-25.
[28] S. Osawa, M. Ho, X. Tanaka, J. Kuwano, J. Polym. Sci. Part B 30 (1992) 19-25.
[29] J.L. Bredas, B. Themans, J.M. Andre, R.R. Chance, R. Silby, Synth. Met. 9 (1984) 265-271.
[30] L. Lauchlan, S. Etamad, T.C. Chung, A.J. Heeger, A.G. MacDiarmid, Phys. Rev. B 24 (1981) 3701-
3710.
[31] T.C. Chung, J.H. Kaufman, A.J. Heeger, F. Wudl, Phys. Rev. B 30 (1984) 702-711.
[32] M.J. Winokur, in Handbook of Conducting Polymers. Conjugated Polymers. Theory, Synthesis,
Properties and Characterisation, 3rd edition, Skotheim, T.A.and.Reynolds, J.R. (Eds.), CRC Press,
Boca Raton, 1 (2007).
[33] M. Zora, I. Ozaka, J. Molecular Struc. 638 (2003) 57-65.
[34] E.K. Gross, R.M. Dreiz, Density Functional Theory; Plenum Press: New York, (1995).
[35] N. Sundaraganesan, H. Umamaheswari, B. Dominic Joshua, M. Ramalingam, J. Molecular Struct.
850 (2008) 84-93.
[36] M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman, V.G.
Zakrazewski, J.A. Montgomery, Jr., R.E. Startmann, J.C. Burant, S. Dapprich, J.M. Millam, A.D.
Daniels, K.N. Kudin, M.C. Strain, O. Farkas, J. Tomasi, V. Barone, M. Cossi, R. Cammi, B.
Mennucci, C. Adamo, S. Clifford, J. Ochterski, G.A. Petersson, P.Y. Ayala, Q.Cui. K. Morokuma,
D.K. Malik, A. D. Rabuck, K. Raghavachar, J.B. Foresman, J. Cioslowski, J.V. Ortiz, B.B. Stefanov,
G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. Gomperts, R.L. Martin, D.J. Fox, T. Keith, M.A.
Al-Laham, C. Y. Peng, A. Nanyakkara, C. Gonzalez, M. Challacombe, P.M.W. Gill, B. Johnson, W.
Chen, M.W. Wong, J.L. Andres,M. Head-Gordon, E. S.Replogle, J.A. Pople, GAUSSIAN 98
(Revision A3), Gaussian Inc, Pittsburgh,PA, (1998).
[37] E.D. Glendening, A.E. Reed, J.E Carpener, F. Weinhold, NBO Version 3.1.
[38] A.E. Reed, L.A. Curtiss, F. Weinhold, Chem. Rev. 88 (1988) 899-907.
[39] J.P. Foster, F. Weinhold, J. Am. Chem. Soc. 102 (1980) 7211-7218; A.E. Reed, L.A. Curtiss, F.
Weinhold, Chem. Rev. 88 (1988) 899-926; F. Weinhold, Natural bond orbital methods, in, P.V.R.
Schleyer, N. L. Allinger, T. Clark, J. Gasteiger, and P. A. Kollman (eds.), Encyclopedia of
Computational Cemistry” (Wiley, Chichester, UK, 1998) Vol. 3, pp. 1792-1811.
[40] H. Sabzyan, A. Omrani, J. Phys. Chem. A 107 (2003) 6476-6480.
[41] A. Omrani, H. Sabzyan, J. Phys. Chem. A 109 (2005) 8874-8879.
[42] M.J. Winokur, in Handbook of Conducting Polymers. Conjugated Polymers. Theory, Synthesis,
Properties and Characterisation, 3rd.edition, Skotheim,T. A. and Reynolds, J. R. (Eds), CRC. Press,
Boca. Raton, 17-1 (2007).
[43] H. Sabzyan, A. Omrani, J. Molecular Struct. 713 (2005) 43-49.
[44] U. Salzner, J.B. Lagowski, P.G. Pickup, R.A. Poirier, Synth. Met. 98 (1998) 177-189.
[45] M. Holb, P. Ehrilich, J. Polym. Sci. 15 (1977) 627-635.
[46] Y.W. Park, M.A. Druy, C.K. Chiang, A.G. MacDiarmid, A.J. Heeger, H. Shirakawa, S. Ikeda, J.
Poly. Sci. 17 (1979) 195-204.
