Ferrocenyl Monomers and Polymers of N-Allyl and N-Acrylatenaphthalimides

  • Bogdan H. Dana
  • C. John McAdam
  • Brian H. Robinson
  • Jim Simpson
  • Hongsheng Wang


A series of N-allyl, N-ethylmethacrylate and N-phenylmethacrylatenaphthalimide monomers have been prepared with –C=CFc, –C≡CFc and –C≡CSiMe3 substituents at the 4-position of the naphthalimide ring. All have been characterised by elemental analysis and spectroscopy; the X-ray structure of N-allyl-4-ethenylferrocenylnapththalimide is also reported. Free-radical polymerisation of these monomers gave homopolymers, random co- and terpolymers with polydispersities ranging from 1.7 to 3.2. Incorporation into a polymer matrix has no effect on the spectroscopic and electrochemical properties of the naphthalimide or ferrocenyl components. The ferrocenyl polymers are electrochromic and when oxidised give naphthalimide\({\rightarrow \hbox{Fc}^{+}}\) charge-transfer bands in the NIR; this electrochromism was examined by OTTLE techniques.


ferrocenyl trimethylsilyl acrylate allyl polymers 



This work was supported by a grant from the New Economy Research Fund of the New Zealand Foundation for Research Science and Technology. We also thank the New Zealand Foundation for Research Science and Technology for a Postdoctoral Fellowship to C.J.M.


  1. 1.
    (a) J. Morgado, J. Gruner, S. P. Walcott, T. M. Yong, R. Cervini, S. C. Moratti, A. B. Holmes, and R. H. Friend, Synth. Metals, 95, 113 (1998). (b) F. Cacialli, C.-M. Bouche, P. Le Barny, R. H. Friend, H. Facoetti, F. Soyer, and P. Robin, Opt. Mater. 9, 163 (1998)Google Scholar
  2. 2.
    (a) W. W. Stewart, Nature, 292, 17 (1981). (b) R. J. Hodgkiss, G. W. Jones, A. Long, R. W. Middleton, J. Parrick, M. R. L. Stratford, P. Wardman, and G. D. Wilson, J Med. Chem. 34, 2268 (1991). (c) Z.-R. Liu, K. H. Hecker, and R. L. Rill, J. Biomol. Struct. Dyn. 14, 331 (1996)Google Scholar
  3. 3.
    (a) Z. D. Tul’guk, R. N. Nurmukhametov, V. G. Klimenko, and L. I. Semenova, Khimicheskie Volokna, 5, 16 (1993). (b) T. Cao and S. E. Webber, Macromolecules, 24, 79 (1991). (c) M. Chen, Y. Hu, H. Yan, and Y. Shen, Youji Huaxue, 21, 294 (2001). (d) I. Grabchev, Dyes Pigments, 38, 219 (1998). (e) T. Philipova, I. Karamancheva, and I. Grabchev, Dyes Pigments, 28, 91 (1995). (f) I. Grabchev, I. Moneva, R. Betcheva, and G. Elyashevich, Mat. Res. Innovat. 6, 34 (2002)Google Scholar
  4. 4.
    (a) F. S. Du, H. Cai, Z.-C. Li, and F.-M. Li, J. Polym. Sci. Part A: Polym. Chem. 36, 1111 (1998). (b) I. Grabchev and V. J. Bojinov, Photochem. Photobio. A: Chem. 139, 157 (2001)Google Scholar
  5. 5.
    (a) C. M. Bouche, P. Le Barny, H. Facoetti, and F. Soyer, J. Chimie Phys. Physico-Chimie Biol. 95, 1351 (1998). (b) F. Cacialli, B. Bouche, P. Le Barny, R. H. Friend, H. Facoetti, and F. Soyer, Opt. Mater. 9, 163 (1998). (c) I. Grabchev and J.-M. Chovelon, Polym. Adv. Technol. 14, 601 (2003)Google Scholar
  6. 6.
    Grabchev I., Moneva I., Bojinov V., Guittonneau S. (2000) J. Mat. Chem 10:1291CrossRefGoogle Scholar
  7. 7.
    Philipova T., Grabchev I., Petrov I. (1997) J. Polym. Sci., Part A: Polym. Chem. 35:1069CrossRefGoogle Scholar
  8. 8.
    (a) I. Grabchev and V. Bojinov, Polym. Degrad. Stab. 70, 147 (2000) (b) V. Bojinov and T. Konstantinova, Dyes Pigments 54, 239 (2002)Google Scholar
  9. 9.
    Grabchev I., Chovelon J.-M., Bojinov V., Ivanova G. (2003) Tetrahedron 59:9591CrossRefGoogle Scholar
  10. 10.
    Arimoto F. S., Haven A. C. (1955) J. Am. Chem. Soc. 77:6295CrossRefGoogle Scholar
  11. 11.
    C. U. Pittman, J. Inorg. Organomet. Polym. Mater. 15, 33 (2005); A. S. Abd-El-Aziz, C. E. Carraher, C. U. Pittman, J. E. Sheats, and M. Zeldin, eds., Macromolecules Containing Metal and Metal-Like Elements, Vol. 2 Organoiron Polymers. (John Wiley & Sons Publishers, Hoboken, N. J., 2004)Google Scholar
  12. 12.
    A. S. Abd-El-Aziz, C. E. Carraher, C. U. Pittman, J. E. Sheats, and M. Zeldin, eds. Macromolecules Containing Metal and Metal-Like Elements, Volume 1: A Half-Century of Metal- and Metalloid-Containing Polymers. (John Wiley & Sons Publishers, Hoboken, N. J., 2003)Google Scholar
  13. 13.
    McAdam C. J., Robinson B. H., Simpson J. (2000) Organometallics 19:3644CrossRefGoogle Scholar
  14. 14.
    McAdam C. J., Morgan J. L., Robinson B. H., Simpson J., Rieger P. H., Rieger A. L. (2003) Organometallics 22:5126CrossRefGoogle Scholar
  15. 15.
    Cavigiolio G., Morgan J. L., Robinson B. H., Simpson J. (2004) Aust. J. Chem. 57:885CrossRefGoogle Scholar
  16. 16.
    McAdam C. J., Morgan J. L., Murray R. E., Robinson B. H., Simpson J. (2004) Aust. J. Chem. 57:525CrossRefGoogle Scholar
  17. 17.
    (a) A. H. Flood, C. J. McAdam, K. C. Gordon, H. G. Kjaergaard, A. M. Manning, B. H. Robinson, and J. Simpson, Polyhedron, in press. (b) L. Cuffe, R. D. A. Hudson, J. F. Gallagher, S. Jennings, C. J. McAdam, R. B. Connelly, A. R. Manning, B. H.Robinson, and J. Simpson, Organometallics, 24, 2051 (2005). (c) P. Chandrasekhar, B. J. Zay, G. C. Birur, S. Rawal, E. A. Pierson, L. Kauder, and T. Swanson, Adv. Funct. Mater. 12, 95 (2002).Google Scholar
  18. 18.
    J. M. Warman, R. D. Abellon, and H. J. Verhey, J. Phys. Chem. B, 101, 4913 (1997). (b) B. H. Cumpston, S. P. Ananthavel, and S. Barlow, Nature, 398, 51 (1999)Google Scholar
  19. 19.
    Liu W.-Y., Xu Q.-H., Ma Y.-X., Liang Y.-M., Dong N.-L., Guan D.-P. (2001) J. Organometal. Chem. 625:128CrossRefGoogle Scholar
  20. 20.
    Abram T. S., Watts W. E. (1976) Synth. React. Inorg. Metal-Org. Chem. 6:31Google Scholar
  21. 21.
    Konstantinova T. N., Meallier P., Grabchev I. (1993) Dyes Pigments 22:191CrossRefGoogle Scholar
  22. 22.
    Grayshan P. H., Kadhim A. M., Peters A. T. (1974) J. Heterocyclic Chem. 11:33CrossRefGoogle Scholar
  23. 23.
    SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA, (1999)Google Scholar
  24. 24.
    G. M. Sheldrick, SHELXS-97 A program for the solution of crystal structures from diffraction data and SHELXL-97 A program for the refinement of crystal structures; University of Göttingen, Germany (1997)Google Scholar
  25. 25.
    Easton C. J., Gulbis J. M., Hoskins B. F., Scharfbillig I. M., Tiekink E. R. T. (1992) Z. Kristallogr. 199:249CrossRefGoogle Scholar
  26. 26.
    (a) R. G. Baughman, S. C.Chang, R. E. Utecht, and R. D. Lewis, Acta Crystallogr. C51, 1189 (1995). (b) R. A. Batchelor, C. A. Hunter, and J. Simpson, Acta Crystallogr. C53, 1117 (1997). (c) S. V. Lindeman, I. I. Ponomarev, and A. L. Rusanov, Acta Crystallogr. C51, 2157 (1995). (d) Y. Dromzee, J. Kossanyi, V. Wintgens, P. Valat, L. Biczok, A. Demeter, and T. Z. Berces, Z. Krystallogr. 210, 760 (1995)Google Scholar
  27. 27.
    Janiak C. (2000) J. Chem Soc. Dalton Trans. 3885Google Scholar
  28. 28.
    Spek A. L. (2003) J. Appl. Cryst. 36:7CrossRefGoogle Scholar
  29. 29.
    Pittman C. U., Hirao A. (1978) J. Polym. Sci., Chem. Ed. 16:1197CrossRefGoogle Scholar
  30. 30.
    C. U. Pittman, J. C. Lai, D. P. Vanderpool, M. Good, and R. Prados in Polymer Characterisation: Interdisciplinary Approaches, C. D. Carver, ed. (Plenum Press, NY, 1971)Google Scholar
  31. 31.
    M. George and G. Hayes, J. Polym. Sci. Chem. Ed. 13, 1049 (1976); M. George and G. Hayes, J. Polym. Sci. Chem. Ed. 14, 475 (1976); M. George and G. Hayes, Polymer 15, 394 (1974)Google Scholar

Copyright information

© Springer Science+Business Media, LLC 2007

Authors and Affiliations

  • Bogdan H. Dana
    • 1
  • C. John McAdam
    • 1
  • Brian H. Robinson
    • 1
  • Jim Simpson
    • 1
  • Hongsheng Wang
    • 1
  1. 1.Department of ChemistryUniversity of OtagoDunedinNew Zealand

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