Synthesis and Molecular Weight Dependent Optical Properties of Mono-Alkoxy Substituted Polythiophenes

Abstract

Poly(3-alkoxythiophene)s with moderately high molecular weights, which exhibit good solubility and film-forming ability, were successfully synthesized by the nickel (0) coupling reaction in good yields. The introduction of a branched side chain resulted in a molecular weight higher than that of the straight one. Broad photoluminescence (PL), ranging from 579 to 684 nm, was readily obtained by choosing the appropriate molecular weight sample of a mother polymer. This may provide a new method for evaluating organic luminescent materials.

References

  1. 1

    R. H. Friend, R. W. Gymer, A. B. Holmes, J. H. Burroughes, R. N. Marks, C. Taliani, D. D. C. Bradley, D. A. Dos Santos, J. L. Brédas, M. Lögdlund, and W. R. Salaneck, Nature, 397, 121 (1999).

  2. 2

    D. Fichou, Ed., “Handbook of Oligo- and Polythiophenes”, Wiley-VCH, Weinheim, Germany, 1999.

    Google Scholar 

  3. 3

    M. Berggren, O. Inganäs, G. Gustafsson, J. Rasmusson, M. R. Andersson, T. Hjertberg, and O. Wennerstorm, Nature, 372, 444 (1994).

  4. 4

    M. R. Anderson, O. Thomas, W. Mammo, M. Svensson, M. Theander, and O. Inganäs, J. Mater. Chem., 9, 1933 (1999).

  5. 5

    M. Gross, D. C. Müller, H.-G. Nothofer, U. Scherf, D. Neher, C. Bräuchle, and K. Meerholz, Nature, 405, 661 (2000).

  6. 6

    L. Groenendaal, F. Jonas, D. Freitag, H. Pielartzik, and J. R. Reynolds, Adv. Mater., 12, 481 (2000).

  7. 7

    R. D. McCullough, Adv. Mater., 10, 93 (1998).

  8. 8

    T. Yamamoto, Bull. Chem. Soc. Jpn., 72, 621 (1999).

  9. 9

    T. Yamamoto, A. Kashiwazaki, and K. Kato, Makromol. Chem., 190, 1649 (1989).

  10. 10

    G. Daoust and M. Leclerc, Macromolecules, 24, 455 (1991).

  11. 11

    K. Faïd, R. Cloutier, and M. Leclerc, Macromolecules, 26, 2501 (1993).

  12. 12

    S.-A. Chen and C.-C Tsai, Macromolecules, 26, 2234 (1993).

  13. 13

    M. C. Gallazi, L. Castellani, R. A. Marin, and G. Zerbi, J. Polym. Sci., Part A: Polym. Chem., 31, 3339 (1993).

  14. 14

    T. Yamamoto, M. Omote, Y. Miyazaki, A. Kashiwazaki, B.-L. Lee, T. Kanbara, K. Osakada, T. Inoue, and K. Kubota, Macromolecules, 30, 7158 (1997).

  15. 15

    A. Iraqi, D. Clark, R. Jones, and A. Krier, Synth. Met., 102, 1220 (1999).

  16. 16

    X. Hu and L. Xu, Polymer, 41, 9147 (2000).

  17. 17

    B. M. W. Langeveld-Voss, R. A. J. Jassen, M. P. T. Christiaans, S. C. J. Meskers, H. P. J. M. Dekkers, and E. W. Meijer, J. Am. Chem. Soc., 118, 4908 (1996).

  18. 18

    Y. Watanabe, T. Mihara, and N. Koide, Macromolecules, 30, 1857 (1997).

  19. 19

    T. Yamamoto, A. Morita, Y. Miyazaki, T. Maruyama, H. Wakayama, Z.-H. Zhou, Y. Nakamura, and T. Kanbara, Macromolecules, 25, 1214 (1992).

  20. 20

    T. A. Chen, X. Wu, and R. D. Rieke, J. Am. Chem. Soc., 117, 233 (1995).

  21. 21

    Since mono-alkoxy thiophene is not a symmetrical molecule, there are three relative orientations available when two thiophene rings are coupled between 2- and 5- positions. The polymer may include three possible regiochemical couplings: HT, TT, and HH. The four singlets in the aromatic region of 1H NMR spectroscopy can be attributed to the four kinds of configuration triads: HT–HT, TT–HT, HT–HH, and TT–HH.

  22. 22

    The introduction of the chiral side chain in P3 was aimed at investigating the π-π stacking structure in the aggregates. P3 showed very weak bisignate CD (circular dichroism) signals in the solid film. This result will be published elsewhere.

  23. 23

    Inganäs et al. (see ref 3) pointed out that the reversed addition order (slowly adding the FeCl3 slurry to the monomer dissolved in chloroform) could increase the molecular weight. We carried out the polymerization using the FeCl3 oxidation method at low temperature (0°C) in both the normal and reverse addition orders, but only the insoluble products were obtained. It seems that the FeCl3 oxidation is too strong for the polymerization of the mono-alkoxy substituted thiophenes.

  24. 24

    The emission efficiency in the solid state was decreased mainly due to the interchain interaction. Adopting bulky side chains could be an answer for solving this problem.3

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Zhang, ZB., Fujiki, M. Synthesis and Molecular Weight Dependent Optical Properties of Mono-Alkoxy Substituted Polythiophenes. Polym J 33, 597–601 (2001). https://doi.org/10.1295/polymj.33.597

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Keywords

  • Poly(3-alkoxythiophene)
  • Nickel Catalyst
  • Molecular Weight
  • Optical Properties

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