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Rigid Optical Chromophore: The Photophysical Properties of p-Phenylene Benzobisthiazole Derivative

Published online by Cambridge University Press:  15 March 2011

Seung-Hwan Lee
Affiliation:
Nanotechnology Group, KARC, Communications Research Laboratory, 588-2 Iwaoka, Nishi-ku, Kobe 651-2492, JAPAN
Akira Otomo
Affiliation:
Nanotechnology Group, KARC, Communications Research Laboratory, 588-2 Iwaoka, Nishi-ku, Kobe 651-2492, JAPAN
Tatsuo Nakahama
Affiliation:
Nanotechnology Group, KARC, Communications Research Laboratory, 588-2 Iwaoka, Nishi-ku, Kobe 651-2492, JAPAN
Toshiki Yamada
Affiliation:
Nanotechnology Group, KARC, Communications Research Laboratory, 588-2 Iwaoka, Nishi-ku, Kobe 651-2492, JAPAN
Shiyoshi Yokoyama
Affiliation:
Nanotechnology Group, KARC, Communications Research Laboratory, 588-2 Iwaoka, Nishi-ku, Kobe 651-2492, JAPAN
Shinro Mashiko
Affiliation:
Nanotechnology Group, KARC, Communications Research Laboratory, 588-2 Iwaoka, Nishi-ku, Kobe 651-2492, JAPAN
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Abstract

A novel rigid and planar chromophore, p-phenylene benzobisthiazole unit with donor and acceptor groups, has been synthesized for second-order nonlinear optical applications. The first hyperpolarizability, β, of the nonlinear optical (NLO) chromophore has been measured by a Hyper-Rayleigh Scattering technique at 1064 nm in 1,1,1,3,3,3-hexafluoro-2-propanol solution. The β value of the NLO chromophore is 405E-30 esu, which is about seventeen times that of the p-NA (nitroaniline) value. The chromophore showed good thermal stability up to 330 °C in nitrogen atmosphere.

Type
Research Article
Copyright
Copyright © Materials Research Society 2002

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References

REFERENCES

1. Rao, D. N., Swiatkiewiez, J., Chopra, P., Ghosal, S. K. and Prasad, P. N., Appl. Phy. Lett. 48, 1187 (1986); H. Vanherzeele, J. S. Meth, S. A. Jenekhe and M. F. Roberts, Appl. Phy. Lett. 58, 663 (1991); H. Vanherzeele, J. S. Meth, S. A. Jenekhe and M. F. Roberts, J. Opt. Soc. Am. B. 9, 524 (1992); A. K. Agrawal and S. A. Jenekhe, Chem. Mater. 4, 95 (1992).Google Scholar
2. Hattori, T., Kagawa, K., Kakimoto, M. and Iami, Y., Macromolecules 26, 4089 (1993).Google Scholar
3.Compound 2, BB10.21.4 2,5-Bis[(2-cyanoethyl)thio]-N-(p-dimethylaminobenzyl)-N'-(p-nitrobenzyl)-p-phenylenedia mine, was synthesized by the following procedure: Et3N (0.61 g, 6 mmol) was added to a stirred solution of 1 (2.57 g, 5 mmol) in 20mL of NMP at room temperature under argon. To this solution, 4-dimethylamino benzoyl chloride (1.10 g, 6 mmol) in 10 mL of NMP was slowly added dropwise with vigorous stirring at 0 °C under argon. The mixture was stirred overnight (16 h) from 0 °C to room temperature. The product was isolated by pouring the solution into 900 mL of water. Recrystallization from acetone afforded 2.65 g (92 %) of pure 2 as yellow powder: 1H NMR (DMSO-d 6) δ: 2.78 (t, 2H, J = 6.6 Hz), 2.80 (t, 2H, J = 6.6 Hz), 3.01 (s, 6H), 3.18 (t, 2H, J = 7.2 Hz), 3.19 (t, 2H, J = 7.2 Hz), 6.78 (d, 2H, J = 9.4 Hz), 7.64 (s, 1H), 7.82 (s, 1H), 7.87 (d, 2H, J = 8.8 Hz), 8.23 (d, 2H, J = 8.3 Hz), 8.40 (d, 2H, J = 8.8 Hz), 9.65 (s, 1H), 10.43 (s, 1H); 13C NMR (DMSO-d 6) δ: 17.83, 29.49, 42.15, 111.48, 119.65, 124.24, 127.05, 128.56, 129.73, 131.40, 134.58, 137.67, 140.26, 149.91, 153.14, 164.69, 165.68. MS m/z ESI: simulated: 574.15, exp. 597.70 (M+Na)+.Google Scholar
4.Compound 3, 2-(4-dimethylaminophenyl)-6-(4-nitrophenyl)benzo(1,2-d:4,5-d')bisthiazole, was synthesized by the following procedure: 2 (0.57 g, 1 mmol) was added to a stirred solution of 0.4 g of P2O5 in 2 mL of methanesulfonic acid at room temperature under argon. The mixture was heated at 80 °C for 12 h, 100 °C for 12 h and further at 120 °C for 12h. The solution was cooled to room temperature and poured into ice water. The solid mixture was neutalized with saturated aqueous NaHCO3. The resulting precipitate was collected by filtration and washed with water/methanol. The crude product was purified by recrystallization from dimethylsulfoxide (DMSO) to give the required chromophore 0.16 g (38 %): 1H NMR (CF3COOD) δ: 3.61 (s, 6H), 8.11 (d, 2H, J = 7.7 Hz), 8.44 (d, 2H, J = 8.8 Hz), 8.51 (d, 2H, J = 7.7 Hz), 8.65 (d, 2H, J = 8.8 Hz), 9.22 (s, 1H), 9.29 (s, 1H); 13C NMR (CF3COOD) δ: 47.01, 114.31, 122.41, 125.15, 129.37, 129.84, 131.42, 132.89, 133.20, 134.32, 143.05, 144.70, 146.85, 151.20, 175.29. MS m/z MALDI - TOF (HABA matrix): simulated: 432.07, exp. 431.34 (M+ - 2CH3).Google Scholar
5. Clays, K. and Persoons, A., Phys. Rev. Lett. 66, 2980 (1991).Google Scholar
6. Clays, K. and Persoons, A., Rev. Sci. Instrum. 63, 3285 (1992).Google Scholar
7. Oudar, L. and Chemla, D. S., J. Chem. Phys. 66, 2664 (1977).Google Scholar