Design of novel nonlinear optical chromophores with multiple substitutions

Abstract

The molecular first hyperpolarizabilities (β) and electronic properties of some tetra-substituted benzenes/pyrazines which can be described as 1,2-didonor-4,5-diacceptor-benzenes/2,3-didonor-5,6-diacceptor-pyrazines have been investigated by employing an AM1/FF and ZINDO/S-CI approach. It is found that these multiple substituted chromophores possess large β values which may be attributed to the positive contribution of the off-diagonal tensorial component β_xyy. Two novel chromophores (1 and 2) containing lengthened conjugation and thermally stable imidazole rings are designed under such a multiple substitutions principle. Chromophore 1 shows a very large µβ₀ value of approximately 3900×10^-48 esu.† The theoretical calculation and preliminary experimental results indicate that a good nonlinearity–transparency–thermal stability trade-off is achieved for chromophore 2, which possesses a µβ₀ of 555×10^-48 esu, a rather blue-shifted absorption peak at 384 nm in THF and a high decomposition temperature (T_d) of 377°C.

References

1. P. N. Prasad and D. J. Williams, Introduction to Nonlinear Optical Effects in Organic Molecules and Polymers, Wiley, New York, 1991.
2. Nonlinear Optical Properties of Organic Molecules and Crystals, ed. D. S. Chemla and J. Zyss, Academic Press, New York, 1987, vol. 1 and 2.
3. Materials for Nonlinear Opticals: Chemical Perspectives, ed. S. R. Marder, J. E. Sohn and G. D. Stucky, ACS Symposium Series 455, American Chemical Society, Washington, DC, 1991.
4. D. R. Kanis, M. A. Ratner and T. J. Marks, Chem. Rev., 1994, 94, 195.
5. L.-T. Cheng, W. Tam, S. Stevenson, G. R. Meredith, G. Rikken and S. R. Marder, J. Phys. Chem., 1991, 95, 10631.
6. L.-T. Cheng, W. Tam, S. R. Marder, A. E. Steigman, G. Rikken and C. W. Spangler, J. Phys. Chem., 1991, 95, 10643.
7. S. R. Marder, J. W. Perry, G. Bourhill, C. Gorman, B. Tiemann and K. Mansour, Science, 1993, 261, 186.
8. N. Matsuzawa and D. A. Dixon, J. Phys. Chem., 1992, 96, 6232.
9. B. Beck and U.-W. Grummt, J. Phys. Chem. B, 1998, 102, 664.
10. S. R. Marder, C. B. Gorman, B. G. Tiemann and L.-T. Cheng, J. Am. Chem. Soc., 1993, 115, 2524.
11. S. R. Marder, D. N. Beratan and L.-T. Cheng, Science, 1991, 252, 103.
12. V. P. Rao, A. K.-Y. Jen, K. Y. Wong and K. J. Drost, Tetrahedron Lett., 1993, 34, 1747.
13. K. Y. Wong, A. K.-Y. Jen, V. P. Rao and K. J. Drost, J. Chem. Phys., 1994, 100, 6818.
14. V. P. Rao, A. K.-Y. Jen, J. Chandrasekhar, I. N. N. Namboothiri and A. Rathna, J. Am. Chem. Soc., 1996, 118, 12443.
15. S. R. Marder, L.-T. Cheng, B. G. Tiemann, A. C. Friedli, M. Blanchard-Desce, J. W. Perry and J. Skindhoy, Science, 1996, 271, 335.
16. C. R. Moylan, R. J. Twieg, V. Y. Lee, S. A. Swanson, K. M. Batterton and R. D. Miller, J. Am. Chem. Soc., 1993, 115, 12599.
17. I. D. L. Albert, T. J. Marks and M. A. Ratner, J. Am. Chem. Soc., 1997, 119, 6575.
18. I. D. L. Albert, T. J. Marks and M. A. Ratner, Chem. Mater., 1998, 10, 753.
19. I. D. L. Albert, T. J. Marks and M. A. Ratner, J. Am. Chem. Soc., 1997, 119, 3155.
20. I. D. L. Albert, T. J. Marks and M. A. Ratner, J. Am. Chem. Soc., 1998, 120, 11174.
21. K. D. Singer, J. F. Sohn, L. A. King, H. M. Gordon, H. E. Katz and C. W. Dirk, J. Opt. Soc. Am. B, 1989, 6, 1339.
22. L. R. Dalton, A. W. Harper, R. Ghosn, W. H. Steier, M. Ziari, H. Fetterman, Y. Shi, R. V. Mustacich, A. K.-Y. Jen and K. J. Shea, Chem. Mater., 1995, 7, 1060.
23. A. W. Harper, L. R. Dalton, S. M. Garner, A. Chen, S. Kalluri, W. H. Steier and B. H. Robinson, J. Opt. Soc. Am. B, 1998, 15, 329.
24. J. Zyss and I. Ledoux, Chem. Rev., 1994, 94, 77.
25. J. Zyss, J. Chem. Phys., 1993, 98, 6583.
26. X. T. Tao, T. Watanabe, S. Shimoda, D. C. Zou, H. Sato and S. Miyata, Chem. Mater., 1994, 6, 1961.
27. S. Ermer, D. G. Girton, D. S. Leung, S. M. Lovejoy, J. F. Valley, T. E. Van Eck and L.-T. Cheng, Nonlinear Opt., 1995, 9, 259.
28. C. R. Moylan, S. Ermer, S. M. Lovejoy, I. McComb, D. S. Leung, R. Wortmann, P. Krdmer and R. J. Twieg, J. Am. Chem. Soc., 1996, 118, 12950.
29. H. S. Nalwa, K. Nakajima, T. Watanabe, K. Nakamura, A. Yamada and S. Miyata, Jpn. J. Appl. Phys., 1991, 30, 983.
30. H. S. Nalwa, T. Watanabe and S. Miyata, Adv. Mater., 1995, 7, 754.
31. J. S. M. Dewar, E. G. Zoebisch, F. Healy and J. J. P. Stewart, J. Am. Chem. Soc., 1985, 107, 3902.
32. J. J. P. Stewart, QCPE Program 455, 1983; Version 6.0 ( 1990).
33. A. Willetts, J. E. Rice, D. M. Burland and D. P. Shelton, J. Chem. Phys., 1992, 97, 7590.
34. B. J. Orr and J. F. Ward, Mol. Phys., 1971, 20, 513.
35. J. E. Ridly and M. C. Zerner, Theor. Chim. Acta, 1976, 42, 223.
36. M. Numan, H. Schenk and D. Dopp, Acta Crystallogr., Sect. C, 1995, 51, 260.
37. J. F. Nicoud and R. J. Twieg, in ref. 2, vol. 1, p. 227.
38. R. W. Munn, N. S. Munn and K. J. Hardie, Adv. Mater. Opt. Electron., 1994, 4, 19.
39. A. Ulman, J. Phys. Chem., 1988, 92, 2385.
40. (a) O. Exner, Correlation Analysis of Chemical Data, Plenum Press, New York, 1988, pp. 61–62; (b) ibid, pp. 143–144.
41. M. Tomonari, N. Ookubo and T. Takada, Chem. Phys. Lett., 1993, 215, 45.
42. M. Tomonari, N. Ookubo and T. Takada, Chem. Phys. Lett., 1995, 236, 475.
43. M. Tomonari, N. Ookubo and T. Takada, Synth. Met., 1996, 81, 137.
44. J. L. Oudar and D. S. Chemla, J. Chem. Phys., 1977, 66, 2664.
45. J. L. Bredas, F. Meyers, B. M. Pierce and J. Zyss, J. Am. Chem. Soc., 1992, 114, 4928.
46. C. Ye, Z. M. Feng, Y. J. Chen, J. F. Wang and H. O. Dong, Chin. Chem. Lett., 1991, 2, 765.
47. S. Miyata and X. T. Tao, Synth. Met., 1996, 81, 99.