Journal of Inorganic and Organometallic Polymers

, Volume 4, Issue 3, pp 237–250 | Cite as

Synthesis and characterization of soluble (porphyrinato)iron(II) polymers

  • Jürgen Pawlik
  • Christian Kautz
  • Martin Baumgarten


The use of (tetrakis(4-hexylphenyl)porphyrinato)Fe(II) in polymerization reactions with bidentate ligands such as 9,10-diisocyanoanthracene and 1,4-diisocyanobenzene led to well-defined stacked polymers1 and2 which are still soluble in common organic solvents such as chloroform, dichloromethane, and tetrahydrofurane. They have been completely characterized by1H-NMR and UV/vis spectropscopy in solution, even allowing end-group analysis for determination of the average degree of polymerization, yieldingn=10 andn=5 for1 and2, respectively. Mößbauer and IR spectroscopy further established the strong Fe-CN bonding reflected by very small isomer shifts and quadrupole splittings (ΔEQ∼0.2 mm s−1) and a large decrease in the IR stretching frequency (ΔvCN∼60 cm−1). The axially stacked polymers exhibit semiconducting properties only upon doping.

Key words

Porphyrinato metal polymers iron(II) complexes isocyanide ligands nuclear magnetic resonance spectroscopy Mößbauer spectroscopy 57Fe 


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. 1. (a)
    R. Comes, P. Bernier, J. J. Andre, and J. Rouxel,Proceedings of the International Conference on Low Dimensional Conductors and Superconductors, Les Arcs-Bourg-Saint-Maurice-Savoie, France, Dec. (1982) [J. Phys. Collog. (1983), C3].Google Scholar
  2. 1. (b)
    H. Schulz, H. Lehmann, M. Rein, and M. Hanack, inStructure and Bonding 74, J. W. Buchler, ed. (Springer, Berlin, 1990), pp. 41–143.Google Scholar
  3. 1. (c)
    J. S. Miller (ed.),Extended Linear Chain Compounds (Plenum, New York, 1982), Vols. 1 and 2.Google Scholar
  4. 2. (a)
    M. Hanack and P. Vermehren,Synth. Met. 32, 257–261 (1988).Google Scholar
  5. 2. (b)
    M. Hanack, S. Deger, and A. Lange,Coord. Chem. Rev. 83, 115 (1988).Google Scholar
  6. 2. (c)
    J. P. Collman, J. T. McDevitt, C. R. Leidner, G. T. Yee, J. B. Torrance, and W. A. Little,J. Am. Chem. Soc. 109, 4606–4614 (1987).Google Scholar
  7. 3.
    M. Hanack, A. Lange, and R. Grosshans,Synth. Met. 45, 59 (1991).Google Scholar
  8. 4. (a)
    O. Schneider and M. Hanack,Mol. Cryst. Liq. Cryst. 81, 273–284 (1982), and references therein.Google Scholar
  9. 4. (b)
    B. N. Diel, T. Inabe, N. Taggi, J. W. Lyding, O. Schneider, M. Hanack, C. R. Kannewurf, T. J. Marks, and L. H. Schwarz,J. Am. Chem. Soc. 106, 3207–3214 (1984).Google Scholar
  10. 5.
    C. E. D. Chidsey and R. W. Murray,Science 231, 25–31 (1986).Google Scholar
  11. 6.
    K. Kaneto, M. Maxfield, D. P. Nairns, A. G. MacDiarmid, and J. A. Heeger,J. Chem. Soc. Faraday Trans. I 78, 3417–3429 (1982).Google Scholar
  12. 7. (a)
    J. P. Collman, J. T. McDevitt, G. T. Yee, and M. B. Zisk,Synth. Met. 15, 129–140 (1986).Google Scholar
  13. 7. (b)
    M. Mezger, M. Hanack, A. Hirsch, J. Kleinwächter, K.-M. Mangold, and L. Ramaswami Subramanian,Chem. Ber. 124, 841–847 (1991).Google Scholar
  14. 8.
    H. Kobayashi and Y. Yanagawa,Bull. Chem. Soc. Jap. 45, 450–456 (1972).Google Scholar
  15. 9.
    M. Hanack and H. Ryu,Synth. Met. 46, 113–126 (1992).Google Scholar
  16. 10. (a)
    F. Calderazzo, S. Frediani, B. R. James, G. Pampaloni, K. J. Reimer, J. R. Sams, A. M. Serra, and O. Vitali,Inorg. Chem. 21, 2302 (1982).Google Scholar
  17. 10. (b)
    B. J. Kennedy, K. S. Murray, P. R. Zwack, H. Homburg, and W. Kalz,Inorg. Chem. 25, 2539 (1986).Google Scholar
  18. 11.
    W. M. Connor and D. K. Straub,Inorg. Chem. 15, 2289 (1976).Google Scholar
  19. 12.
    C. Reichardt,Solvents and Solvent Effects in Organic Chemistry (VCH, Weinheim, Germany, 1988).Google Scholar
  20. 13.
    A. Adler, F. R. Longo, J. D. Finarelli, J. Goldmacher, I. Assur, and K. Korsakoff,J. Org. Chem. 32, 476 (1967).Google Scholar

Copyright information

© Plenum Publishing Corporation 1994

Authors and Affiliations

  • Jürgen Pawlik
    • 1
  • Christian Kautz
    • 2
  • Martin Baumgarten
    • 1
  1. 1.Max-Planck-Institut für PolymerforschungMainzGermany
  2. 2.Mannesmann AGFrankfurt a.M.Germany

Personalised recommendations