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Journal of the Optical Society of America B

Journal of the Optical Society of America B


  • Vol. 15, Iss. 2 — Feb. 1, 1998
  • pp: 846–853

Syntheses and nonlinear optical properties of nonaggregated metallophthalocyanines

Minquan Tian, Suichi Yanagi, Keisuke Sasaki, Tatsuo Wada, and Hiroyuki Sasabe  »View Author Affiliations

JOSA B, Vol. 15, Issue 2, pp. 846-853 (1998)

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Hexadecakis(2, 2, 2-trifluoroethoxy)-substituted vanadyl and zinc phthalocyanines, and hexadecakis(ethoxy)vanadylphthalocyanine, were synthesized and characterized. Their aggregation properties were studied by evaluation of the concentration dependence of absorption spectra. Hexadecakis(2, 2, 2-trifluoroethoxy)-substituted metallophthalocyanines were found to be nonaggregated phthalocyanines even in the condensed state. However, nonfluorinated hexadecakis(ethoxy)vanadylphthalocyanine showed a redshift of the Q band in the solid state. The third-order nonlinear optical properties of these phthalocyanine films were studied by electroabsorption measurement in terms of molecular structure and aggregation. The aggregation effect enhances the macroscopic third-order nonlinearity of metallophthalocyanine. Among nonaggregated hexadecakis(2, 2, 2-trifluoroethoxy)-substituted metallophthalocyanines, zinc phthalocyanine was found to have a larger macroscopic third-order nonlinearity than the vanadyl compound.

© 1998 Optical Society of America

OCIS Codes
(160.0160) Materials : Materials
(190.0190) Nonlinear optics : Nonlinear optics
(190.4710) Nonlinear optics : Optical nonlinearities in organic materials

Minquan Tian, Suichi Yanagi, Keisuke Sasaki, Tatsuo Wada, and Hiroyuki Sasabe, "Syntheses and nonlinear optical properties of nonaggregated metallophthalocyanines," J. Opt. Soc. Am. B 15, 846-853 (1998)

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  1. Z. Z. Ho, C. Y. Ju, and W. M. Hetherington III, “Third harmonic generation in phthalocyanines,” J. Appl. Phys. 62, 716–718 (1987).
  2. T. Wada, Y. Matsuoka, K. Shigehara, A. Yamada, A. F. Garito, and H. Sasabe, “Organic nonlinear thin film: phthalocyanine derivatives,” in Photoresponsive Materials, M. Doyama, S. Somiya, R. P. H. Chang, and S. Tazuke, eds., Mater. Res. Soc. Symp. Proc. 12, 75–80 (1989).
  3. J. L. Brédas, C. Adant, P. Tackx, and A. Persoons, “Third-order nonlinear optical response in organic materials: theoretical and experimental aspects,” Chem. Rev. 94, 243–278 (1994).
  4. N. J. Long, “Organometallic compounds for nonlinear optics—the search for enlightenment,” Angew. Chem. Int. Ed. Engl. 34, 21–38 (1995).
  5. H. S. Nalwa and J. S. Shirk, “Nonlinear optical properties of metallophthalocyanines,” in Phthalocyanines, Properties and Applications, C. C. Leznoff and A. B. P. Lever, eds. (VCH, New York, 1996), Vol. 4, pp. 79–181, and references therein.
  6. H. Tajalli, J. P. Jiang, J. T. Murray, N. R. Armstrong, A. Schmidt, M. Chandross, S. Mazumdar, and N. Peyghambarian, “Spectra of third-order optical nonlinear susceptibilities of epitaxial chloro-indium-phthalocyanines,” Appl. Phys. Lett. 67, 1639–1641 (1995).
  7. M. A. Díaz-García, J. M. Cabrera, F. Agulló-López, J. A. Duro, G. de la Torre, T. Torres, F. Fernández-Lázaro, P. Delhaes, and C. Mingotaud, “Third-order nonlinear optical susceptibilities of the Langmuir–Blodgett films of octa-substituted metallophthalocyanines,” Appl. Phys. Lett. 69, 293–295 (1996).
  8. S. L. Fang, H. Tada, and S. Mashiko, “Enhancement of the third-order nonlinear optical susceptibility in epitaxial vanadyl-phthalocyanine films grown on KBr,” Appl. Phys. Lett. 69, 767–769 (1996).
  9. M. Hosoda, T. Wada, A. Yamada, A. F. Garito, and H. Sasabe, “Phase and third-order optical nonlinearities in tetravalent metallophthalocyanine thin films,” Jpn. J. Appl. Phys. 30, L1486–L1488 (1991).
  10. M. Hosoda, T. Wada, T. Yamamoto, A. Kaneko, A. F. Garito, and H. Sasabe, “Enhancement of third-order optical nonlinearities of soluble vanadyl phthalocyanines in doped polymer films,” Jpn. J. Appl. Phys. 31, 1071–1075 (1992).
  11. A. Terasaki, M. Hosoda, T. Wada, H. Tada, A. Koma, A. Yamada, H. Sasabe, A. F. Garito, and T. Kobayashi, “Femtosecond spectroscopy of vanadyl phthalocyanines in various molecular arrangements,” J. Phys. Chem. 96, 10534–10542 (1992).
  12. E. S. Dodsworth, A. B. P. Lever, P. Seymour, and C. C. Leznoff, “Intramolecular coupling in metal-free binuclear phthalocyanine,” J. Phys. Chem. 89, 5698–5705 (1985).
  13. H. Kobayashi, K. Matsumoto, and T. Sonoda, “Active transport of alkali metal ions under two-phase conditions. Synthesis and application of highly lipophilic phthalocyanines with a large number of pendant polyfluoroalkoxyl groups,” in Proceedings of the 2nd International Symposium on the Chemistry of Functional Dyes (Mita, Osaka, Japan, 1992), pp. 290–295.
  14. T. Wada and H. Sasabe, “Metallophthalocyanine: aggregation and nonlinear optics,” in Organic, Metallo-Organic, and Polymeric Materials for Nonlinear Optical Applications, S. R. Marder and J. W. Perry, eds., Proc. SPIE 2143, 164–171 (1994).
  15. T. Isoshima, N. Pfeffer, M. Tian, T. Wada, and H. Sasabe, “Polarization dependence of transient absorption change in a vanadylphthalocyanine,” in Nonlinear Optical Properties of Organic Materials IX, G. R. Möhlmann, ed., Proc. SPIE 2852, 211–219 (1996).
  16. J. W. Perry, K. Mansour, I.-Y. S. Lee, X.-L. Wu, P. V. Bedworth, C.-T. Chen, D. Ng, S. R. Marder, P. Miles, T. Wada, M. Tian, and H. Sasabe, “Organic optical limiter with a strong nonlinear absorptive response,” Science 273, 1533–1536 (1996).
  17. M. Tian, T. Wada, and H. Sasabe, “Synthesis of unsymmetrically substituted dodecakis(trifluoroethoxy)phthalo cyaninato vanadyl complexes,” J. Heterocyc. Chem. 34, 171–176 (1997).
  18. W. Eberhardt and M. Hanack, “Synthesis of hexadeca alkoxy-substituted nickel and iron phthalocyanines,” Synthesis 95–100 (1997).
  19. A. Kuroiwa, N. Nanba, and T. Kamijo, “Optical recording medium,” Japanese Patent Showa 61–246091, in Kokai Tokkyo Koho A (Japanese Patent Office, Tokyo, 1986), pp. 481–495.
  20. H. Tomoda, S. Saito, S. Ogawa, and S. Shiraishi, “Synthesis of phthalocyanines from phthalonitrile with organic strong base,” Chem. Lett. 1277–1280 (1980).
  21. S. Yanagi, T. Wada, J. Kumar, H. Sasabe, and K. Sasaki, “Electroabsorption spectra and nonlinear optical susceptibility of tetrakis tert-butyl phthalocyanine,” Mol. Cryst. Liq. Cryst. 255, 167–175 (1994).
  22. T. G. Arkatova, N. M. Gopshtein, E. G. Makarova, and B. A. Mikhailov, “Determining the optical constants of a material by means of the Kramers–Kronig relations,” Sov. J. Opt. Technol. 48, 552–562 (1981).
  23. J. S. Weiner, D. A. B. Miller, and D. S. Chemla, “Quadratic electro-optic effect due to the quantum-confined Stark effect in quantum wells,” Appl. Phys. Lett. 50, 842–844 (1987).
  24. R. Worland, S. D. Phillips, W. C. Walker, and A. J. Heeger, “Electroabsorption and nonlinear optical constants of trans-polyacetylene and poly(3-hexylthiophene),” Synth. Met. 28, D663–D667 (1989).
  25. M. Kasha, H. R. Rawls, and M. A. El-Bayoumi, “The exciton model in molecular spectroscopy,” Pure Appl. Chem. 11, 371–392 (1965).
  26. M. Gouterman, D. Holten, and E. Lieberman, “Porphyrins XXXV. Exciton coupling in μ-oxo scandium dimers,” Chem. Phys. 25, 139–153 (1977).
  27. A. J. McHugh, M. Gouterman, and C. Weiss, “Porphyrins XXIV. Energy, oscillator strength, and Zeeman splitting calculations (SCMO-CI) for phthalocyanine, porphyrins and related ring systems,” Theor. Chim. Acta 24, 346–370 (1972).
  28. A. M. Schaffer, M. Gouterman, and E. R. Davidson, “Porphyrins XXVIII. Extended Hückel calculations on metal phthalocyanines and tetrazaporphyrins,” Theor. Chim. Acta 30, 9–30 (1973).
  29. M. Hosoda, T. Wada, A. Yamada, A. F. Garito, and H. Sasabe, “Third-order nonlinear optical properties in soluble phthalocyanines with tert-butyl substituents,” Jpn. J. Appl. Phys. 30, 1715–1719 (1991).
  30. H. S. Nalwa, A. Kakuta, and A. Mukoh, “Third-order optical nonlinearities of tetrakis-n-pentoxy carbonyl metallo-naphthalocyanines,” Chem. Phys. Lett. 203, 109–113 (1993).
  31. J. Simon and J. J. Andre, Molecular Semiconductors (Springer-Verlag, Berlin, 1985).
  32. G. A. Agrawal, C. Cojan, and C. Flytzanis, “Nonlinear optical properties of one-dimensional semiconductors and conjugated polymers,” Phys. Rev. B 17, 776–789 (1978).
  33. M. Sinclair, D. Moses, K. Agagi, and A. J. Heeger, “Aniso-tropy of the third-order nonlinear optical susceptibility in a degenerate-ground-state conjugated polymer: trans- (CH)x,” Phys. Rev. B 38, 10724–10733 (1988).
  34. J. R. Heflin, K. Y. Wong, O. Zamani-Khamiri, and A. F. Garito, “Nonlinear optical properties of linear chains and electron-correlation effects,” Phys. Rev. B 38, 1573–1576 (1988).
  35. J. W. Wu, J. R. Heflin, R. A. Norwood, K. Y. Wong, O. Zamani-Khamiri, A. F. Garito, P. Kalyanaraman, and J. Sounik, “Nonlinear-optical processes in low-dimensional conjugated structures,” J. Opt. Soc. Am. B 6, 707–720 (1989).

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