Advertisement

Clays and Clay Minerals

, Volume 35, Issue 1, pp 53–59 | Cite as

Reactions of Thiophene and Methylthiophenes in the Interlayer of Transition-Metal Ion-Exchanged Montmorillonite Studied by Resonance Raman Spectroscopy

  • Yuko Soma
  • Mitsuyuki Soma
  • Yukio Furukawa
  • Issei Harada
Article

Abstract

The adsorption and reaction of thiophene and methylthiophenes in the interlayer of Cu2+- and Fe3+-montmorillonites were investigated by resonance Raman spectroscopy. Thiophene and 3-methylthiophene polymerized to form cations of polythiophene and polymethylthiophene respectively, which were characterized by absorption bands in the near-infrared region. These polymer cations formed in the interlayer were reduced to their neutral polymers if the clay-polymer complexes were in contact with water, and the formation of their neutral polymers was clearly demonstrated by their resonance Raman spectra. 2,5-Dimethylthiophene in which polymerization was hindered by methyl substitution at the 2 and 5 positions, was oxidized to 2,5-dimethylthiophene cation in the interlayer.

Key Words

Adsorption Interlayer reaction Montmorillonite Polymerization Raman spectroscopy Thiophene 

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. Akimoto, M., Furukawa, Y., Takeuchi, H., and Harada, I. (1984) Vibrational spectra of conjugated conductive polymer: in Proc. Symp. Molecular Structures, Chem. Soc. Japan, Tokyo, 312–313.Google Scholar
  2. Akimoto, M., Furukawa, Y., Takeuchi, H., and Harada, I. (1985) Vibrational spectra of polythiophene: in Proc. 50th Annual Meeting Chem. Soc. Japan, p. 35.Google Scholar
  3. Akimoto, M., Furukawa, Y., Takeuchi, H., Harada, I., Soma, Y., and Soma, M. (1986) Correlation between vibrational spectra and electrical conductivity of polythiophene: Synth. Met. 15, 353–360.CrossRefGoogle Scholar
  4. Bredas, J. L., Chance, R. R., and Silbey, R. (1981) Theoretical study of charged defect states in doped polyacetylene and polyparaphenylene: Mol. Cryst, Liq. Cryst. 77, 319–332.CrossRefGoogle Scholar
  5. Bredas, J. L., Silbey, R., Boudreaux, D. S., and Chance, R. R. (1983) Chain-length dependence of electronic and electrochemical properties of conjugated systems: Polyacetylene, polyphenylene, polythiophene, and polypyrrole: J. Amer. Chem. Soc. 105, 6555–6559.CrossRefGoogle Scholar
  6. Chung, T. C, Kaufman, J. H., Heeger, A. J., and Wudl, F. (1984) Charge storage in poly(thiophene): Optical and electrochemical studies: Phys. Rev. B30, 702–710.Google Scholar
  7. Cloos, P., Vande Poel, D., and Camerlynck, J. P. (1973) Thiophene complexes on montmorillonite saturated with different cations: Nature Phys. Sci. 243, 54–55.CrossRefGoogle Scholar
  8. Mortland, M. M. and Pinnavaia, T. J. (1971) Formation of copper(II)-arene complexes on the interlamellar surfaces of montmorillonite: Nature Phys. Sci. 229, 75–77.CrossRefGoogle Scholar
  9. Pinnavaia, T. J., Hall, P. T., Cady, S. S., and Mortland, M. M. (1974) Aromatic radical cation formation on the intracrystal surfaces of transition metal layer lattice silicates: J. Phys. Chem. 78, 994–999.CrossRefGoogle Scholar
  10. Pinnavaia, T. J. and Mortland, M. M. (1971) Interlameller metal complexes on layer silicates I. Copper(II)-arene complexes on montmorillonite: J. Phys. Chem. 75, 3957–3962.CrossRefGoogle Scholar
  11. Rupert, J. P. (1973) Electron spin resonance spectra of interlamellar copper(II)-arene complexes on montmorillonite: J. Phys. Chem. 77, 784–790.CrossRefGoogle Scholar
  12. Seyama, H. and Soma, M. (1984) X-ray photoelectron spectroscopic study of montmorillonite containing exchangeable divalent cations: J. Chem. Soc, Faraday Trans. 1 80, 237–248.CrossRefGoogle Scholar
  13. Shirakawa, H. and Yamabe, T., eds. (1980) Synthetic metals: Kagaku-dojin, Tokyo, Japan, 182 pp.Google Scholar
  14. Soma, Y., Soma, M., and Harada, I. (1983a) Raman spectroscopic evidence of formation of p-dimethoxybenzene cation on Cu- and Ru-montmorillonites: Chem. Phys. Lett. 94, 475–478.CrossRefGoogle Scholar
  15. Soma, Y., Soma, M., and Harada, I. (1983b) Resonance Raman spectra of benzene adsorbed on Cu2+-montmorillonite. Formation of poly(p-phenylene) cations in the interlayer of the clay mineral: Chem. Phys. Lett. 99, 153–156.CrossRefGoogle Scholar
  16. Soma, Y., Soma, M., and Harada, I. (1984) The reaction of aromatic molecules in the interlayer of transition-metal ionexchanged montmorillonite studied by resonance Raman spectroscopy. 1. Benzene and p-phenylenes: J. Phys. Chem. 88, 3034–3038.CrossRefGoogle Scholar
  17. Soma, Y., Soma, M., and Harada, I. (1985) Reactions of aromatic molecules in the interlayer of transition-metal ion-exchanged montmorillonite studied by resonance Raman spectroscopy. 2. Monosubstituted benzenes and 4,4’-disubstituted biphenyls: J. Phys. Chem. 89, 738–742.CrossRefGoogle Scholar
  18. Tourillon, G. and Garnier, F. (1983) Effect of dopant on the physicochemical and electrical properties of organic conducting polymers: J. Phys. Chem. 87, 2289–2292.CrossRefGoogle Scholar
  19. Tourillon, G., Gourier, D., Garnier, P., and Vivien, D. (1984) Electron spin resonance study of electrochemically generated polythiophene and derivatives: J. Phys. Chem. 88, 1049–1051.CrossRefGoogle Scholar
  20. Yong, C. and Renyuan, Q. (1985) IR and Raman studies of polythiophene prepared by electrochemical polymerization: Solid State Communi. 54, 211–213.CrossRefGoogle Scholar

Copyright information

© The Clay Minerals Society 1987

Authors and Affiliations

  • Yuko Soma
    • 1
  • Mitsuyuki Soma
    • 1
  • Yukio Furukawa
    • 2
  • Issei Harada
    • 2
  1. 1.National Institute for Environmental StudiesYatabe, Tsukuba, IbarakiJapan
  2. 2.Pharmaceutical InstituteTohoku UniversityAobayama, SendaiJapan

Personalised recommendations