Bathochromic or hypsochromic effects via the extension of conjugation: a study of stilbenoid squaraines

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Herbert Meier, Ralf Petermann and Jürgen Gerold


Abstract

In contrast to normal conjugated oligomers, the stilbenoid squaraines 3a–d do not show a convergence of VIS/NIR absorption due to the extension of conjugation; the observed bathochromic effect in the beginning of the series is followed by a hypsochromic effect; this result seems to be characteristic for stilbenoid compounds with donor–acceptor substitution.


References

  1. K. Y. Law, Chem. Rev., 1993, 93, 449 CrossRef CAS and references therein.
  2. A. H. Schmidt, in Oxocarbons, ed. R. West, Academic Press, New York, 1980, p. 185 Search PubMed.
  3. M. Emmelius, G. Pawlowski and H. W. Vollmann, Angew. Chem., 1989, 101, 1475; Angew. Chem., Int. Ed. Engl., 1989, 28, 1445 Search PubMed.
  4. C.-T. Chen, S. R. Marder and L. T. Cheng, J. Chem. Soc., Chem. Commun., 1994, 259 RSC; J. Am. Chem. Soc., 1994, 116, 3117 Search PubMed.
  5. G. J. Ashwell, G. Gefferies, D. G. Hamilton, D. E. Lynch, M. P. S. Roberts, G. S. Bahra and C. R. Brown, Nature, 1995, 375, 385 CrossRef CAS.
  6. R. O. Loutfy, C. K. Hsiao and P. M. Kazmaier, Photogr. Sci. Eng., 1983, 27, 5 Search PubMed.
  7. H. Meier and U. Dullweber, J. Org. Chem., 1997, 62, 4821 CrossRef CAS.
  8. Selected data for 3a: mp 92 °C; δH(CDCl3) 0.86 (t, 24 H, CH3), 1.24 (m, 80 H, CH2), 1.84 (m, 4 H, CH), 3.26 (d, 8 H, NCH2), 5.79 (s, 4 H, arom. H), 10.94 (s, 4 H, OH). For 3b: mp 169 °C; δH(CDCl3) 0.86 (t, 24 H, CH3), 1.24 (m, 80 H, CH2), 1.82 (m, 4 H, CH), 3.23 (d, 8 H, NCH2), 6.48 (s, 4 H, arom. H), 6.61/7.39 (AA′BB′, 8 H, arom. H), 6.70/7.31 (AB, 3J 15.8, olefin H), 11.02 (s, 4 H, OH). For 3c: mp 220–225 °C; δH(CDCl2–CDCl2, 315 K) 0.83 (t, 24 H, CH3), 1.20 (m, 80 H, CH2), 1.75 (m, 4 H, CH), 3.10 (d, 8 H, NCH2), 6.42 (s, 4 H, arom. H), 6.54/7.23 (AA′BB′, 8 H, arom. H), 6.70/6.96 (AB, 3J 16.1, 4 H, olefin H), 6.74/7.18 (AB, 3J 15.8, 4 H, olefin H), 7.34/7.38 (AA′BB′, 8 H, arom. H), 10.88 (s, 4 H, OH). For 3d: mp 245 °C (decomp.); δH(CDCl2–CDCl2, 313 K) 0.84 (t, 24 H, CH3), 1.20 (m, 80 H, CH2), 1.73 (m, 4 H, CH), 3.29 (d, 8 H, NCH2), 6.47 (s, 4 H, arom. H), 6.51 (m, 4 H, arom. H), 6.79–7.25 (m, 12 H, olefin H), 7.33–7.60 (m, 20 H, arom. H), 10.95 (br s, 4 H, OH).
  9. H. Meier, U. Stalmach and H. Kolshorn, Acta Polym., 1997, 48, 379 CrossRef CAS.
  10. The Δν values are in both series of comparable size.
  11. C. Laurence, J. Phys. Chem., 1994, 23, 5807 CrossRef.
  12. H. Grün and H. Görner, J. Phys. Chem., 1989, 20, 7144 CrossRef.
  13. G. Manecke and S. Lüttke, Chem. Ber., 1970, 103, 700 CAS.
  14. See also W. T. Simpson, J. Am. Chem. Soc., 1951, 73, 5359 and 5326 Search PubMed.
  15. P. Rys and H. Zollinger, Farbstoffchemie, Verlag Chemie, 1982, p. 91 Search PubMed.
  16. The enhanced polarity of the S1 state compared to the ground state S0 is proved by a pronounced positive solvatochromic effect; 3b for example has an absorption maximum in cyclohexane at 840 and in CH2Cl2 at 911 nm.
  17. R. W. Bigelow and H.-J. Freund, Chem. Phys., 1986, 107, 159 CrossRef CAS.
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