Synthesis and Properties of Novel Crosslinkable Phthalocyanine Monomers


Polymer films incorporating phthalocyanine rings are useful for third-order nonlinear optical applications. Two axially modified silicon phthalocyanine monomers containing crosslinkable sites have been synthesized. A monomer containing acrylate groups was crosslinked thermally whereas a monomer containing cinnamate groups was crosslinked both thermally and photochemically. Both monomers can be made into solid polymeric films incorporating over 20% (w/w) of the phthalocyanine ring with no observable phase segregation. Elemental analysis, 1H NMR, FT-IR, and UV-Vis spectroscopy were employed for the structural characterization of the monomers. The kinetics of crosslinking such as reaction conversion versus time and temperature, heat of reaction (ΔH), activation energy (ΔE) and reaction order (n), and the thermal properties of the crosslinked films have also been investigated.


  1. 1

    Z. Z. Ho, C. Y. Ju, and W. M. Hetherington, J. Appl. Phys., 62, 716 (1987).

  2. 2

    J. W. Wu, J. R. Helfin, R. A. Norwood, K. Y. Wong, O. Zamani-Khamiri, A. F. Garito, P. Kalyanaraman, and J. Sounik, J. Opt. Soc. Am., B6, 707 (1989).

  3. 3

    J. S. Shirk, J. R. Lindle, F. J. Bartoli, Z. H. Kafafi, and A. W. Snow, in “New Materials for Nonlinear Optics,” S. R. Marder, J. E. Sohn, and G. D. Stucky, Ed., American Chemical Society, Washington, D.C., 1991.

    Google Scholar 

  4. 4

    M. Hosoda, T. Wada, T. Yamamoto, A. Kaneko, A. F. Garito, and H. Sasabe, Jpn. J. Appl. Phys., 31, 1071 (1992).

  5. 5

    H. S. Nalwa, Adv. Mater., 5, 341 (1993).

  6. 6

    H. S. Nalwa, A. Kakuta, and A. Mukoh, Chem. Phy. Lett., 203, 109 (1993) and references therein.

  7. 7

    N. Q. Wang, Y. M. Cai, J. R. Helfin, and A. F. Garito, Mol. Cryst. Liq. Cryst., 189, 39 (1990).

  8. 8

    H. S. Nalwa, A. Kakuta, and A. Mukoh, J. Phys. Chem., 97, 1097 (1993).

  9. 9

    H. S. Nalwa, Appl. Organomet. Chem., 5, 349 (1991).

  10. 10

    J. S. Shirk, J. R. Lindle, F. J. Bartoli, Z. H. Kafafi, A. W. Snow, and M. Boyle, Int. J. Nonlinear Opt. Phys., 1, 699 (1992).

  11. 11

    J. S. Shirk, J. R. Lindle, F. J. Bartoli, and M. E. Boyle, Int. J. Phys. Chem., 96, 5847 (1992).

  12. 12

    H. Hoshi, K. Kohama, S. Fang, and Y. Maruyama, Appl. Phys. Lett., 63, 3080 (1993).

  13. 13

    R. A. Norwood and J. R. Sounik, Appl. Phys. Lett., 60, 295 (1992).

  14. 14

    J. R. Sounik, G. Khanarian, J. Popolo, and S. Meyer, Chem. Mater., 5, 1253 (1993).

  15. 15

    R. D. Joyner and M. E. Kenney, Inorg. Chem., 1, 236 (1962).

  16. 16

    I. McCulloch, H.-T. Man, B. Marr, C. C. Teng, and K. Song, Chem. Mater., 6, 611 (1994).

  17. 17

    M. Hanack, A. Gul, A. Hirsch, B. K. Mandal, L. R. Subramanian, and E. Witke, Mol. Cryst. Liq. Cryst., 187, 365 (1990).

  18. 18

    C. Xu, B. Wu, O. Todorova, L. R. Dalton, Y. Shi, P. M. Ranon, and W. H. Steier, Macromolecules, 26, 5303 (1993).

  19. 19

    H. R. Allcock and C. G. Cameron, Macromolecules, 27, 3125 (1994).

  20. 20

    E. A. Cuellar and T. J. Marks, Inorg. Chem., 20, 3766 (1981).

  21. 21

    V. Ahsen, E. Yilmazer, M. Ertas, and O. Bekaroblu, J. Chem. Soc., Dalton Trans., 401 (1988).

  22. 22

    M. J. Cook, A. J. Dunn, S. D. Howe, and A. J. Thomson, J. Chem. Soc., Perkin Trans. 1, 2453 (1988).

  23. 23

    B. K. Mandal, J. Kumar, J.-C. Huang, and S. Tripathy, Makromol. Chem., Rapid. Commun., 12, 63 (1991).

Download references

Author information



Rights and permissions

Reprints and Permissions

About this article

Cite this article

Mandal, B., Sinha, A. & Kamath, M. Synthesis and Properties of Novel Crosslinkable Phthalocyanine Monomers. Polym J 27, 529–535 (1995).

Download citation


  • Crosslinkable Phathalocyanine
  • Third-Order Nonlinear Optical Properties
  • Thermal and Photochemical Crosslinking Reactions

Further reading