Poly(3′,4′-[bis(N,N′-ethyloxamyl)]terthiophene): A new functionalized conductive polymer with tunable pendent ethyloxamyl substituents

Abstract

The electrosynthesis and the properties of a new functionalized polythiophene poly(3′,4′-[bis(N,N′-ethyloxamyl)]terthiophene) possessing a complexing cavity grafted onto one in three thiophene units are studied. The polymer has been characterized by means of several spectroscopic techniques (IR, Raman, XPS). It exhibits the usual behavior of the polythiophene class of material. Furthermore, it can be chemically modified, replacement of ester by amide groups in the solid state being evidenced by XPS and IR spectroscopy. The influence of the switching reaction of the polythiophene backbone upon the microscopic properties of the pendent ethyloxamyl groups is studied. IR spectroscopy and molecular modeling indicate that the π-electron density and the size of the complexing active center depend on the applied potential.

References

1. K. Kaeriyama, in Handbook of Organic Conductive Molecules and Polymers, ed. H. S. Nalwa, Wiley and Sons, New York, 1997, vol. 2, p. 271.
2. R. D. McCullough, Adv. Mater., 1998, 10, 93.
3. S. J. Higgins, Chem. Soc. Rev., 1997, 26, 247.
4. R. D. McCullough and S. P. Williams, J. Am. Chem. Soc., 1993, 115, 11608.
5. (a) E. M. Genies, A. A. Syed and M. Salmon, Synth. Met., 1985, 11, 353; (b) M. Sato, S. Tanaka and K. Kaeriyama, J. Chem. Soc., Chem. Commun., 1987, 1725.
6. D. J. Guerrero, X. Ren and J. P. Ferraris, Chem. Mater., 1994, 6, 1437.
7. G. Zotti, S. Zecchin, G. Schiavon, A. Berlin, G. Pagani and A. Kanavesi, Chem. Mater., 1995, 7, 2309.
8. S. Zhu and T. M. Swager, J. Am. Chem. Soc., 1996, 118, 3777.
9. B. Wang and M. R. Wasielewski, J. Am. Chem. Soc., 1996, 118, 8713.
10. J. L. Reddinger and J. R. Reynolds, Macromolecules, 1997, 30, 673; Chem. Mater., 1998, 10, 1236.
11. M. O. Wolf and M. S. Wrighton, Chem. Mater., 1994, 6, 1526.
12. C. Mangeney, J. C. Lacroix, S. Aeiyach, M. Jouini, K. I. Chane-Ching and P. C. Lacaze, J. Chim. Phys., 1998, 95, 1535.
13. J. Li and K. Aoki, J. Electroanal. Chem., 1998, 458, 155.
14. C. Kitamura, S. Tanaka and Y. Yamashita, Chem. Mater., 1996, 8, 570.
15. (a) M. C. Pham, F. Adami, P. C. Lacaze, J. P. Doucet and J. E. Dubois, J. Electroanal. Chem., 1986, 201, 413; (b) M. C. Pham, F. Adami and P. C. Lacaze, J. Electroanal. Chem., 1989, 265, 247.
16. Gaussian 94, Revision E.1: M. J. Frisch, G. W. Trucks, H. B. Schlegel, P. M. W. Gill, B. G. Johnson, M. A. Robb, J. R. Cheeseman, T. Keith, G. A. Peterson, J. A. Montgomery, K. Raghavachari, M. A. Al-Laham, V. G. Zakrzewski, J. V. Ortiz, J. B. Foresman, J. Cioslowski, B. B. Stefanov, A. Nanayakkara, M. Challacombe, C. Y. Peng, P. Y. Ayala, W. Chen, M. W. Wong, J. L. Andres, E. S. Replogle, R. Gomperts, R. L. Martin, D. J. Fox, J. S. Binkley, D. J. Defrees, J. Baker, J. P. Stewart, M. Head-Gordon, C. Gonzalez and J. A. Pople, Gaussian, Inc., Pittsburgh PA, 1995.
17. G. Beamson and D. Brigs, High Resolution XPS of Organic Polymers, Wiley and Sons, Chichester, 1992.
18. Y. Furukuwa, M. Akimoto and I. Harada, Synth. Met., 1987, 18, 151.
19. (a) D. Lin-Vien, N. B. Colthup, W. G. Fateley and J. G. Grasseli, The Handbook of IR and Raman Characteristic Frequencies of Organic Molecules, Academic Press, New York, 1991, p. 143; (b) L. J. Bellamy, The IR Spectra of Complex Molecules, Wiley and Sons, New York, 2nd edn., 1959, p. 203.
20. M. Akimoto, Y. Furukawa, H. Takeuchi, I. Harada, Y. Soma and M. Soma, Synth. Met., 1986, 15, 353.
21. Aldrich data base, R. E. Richard and H. W. Thompson, J. Chem. Soc., 1947, 1248.
22. A. D. Becke, J. Chem. Phys., 1993, 98, 5648.
23. A. P. Scott and L. Radom, J. Phys. Chem., 1996, 100, 16502.
24. G. Rauhut and P. Pulay, J. Phys. Chem., 1995, 99, 3093.