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Large second-order optical nonlinearities of s-triazine derivatives: View from micro molecules to macro crystals

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Abstract

Three s-triazine derivatives have been synthesized and their structures been determined. These are Compound I: 2,4-dimethyl-6-(p-N,N-dimethylaminostyryl)-s-triazine (abbreviated to NMe-1), Compound II: 2,4-dimethyl-6-(p-N,N-diethylaminostyryl)-s-triazine (to NEt-1), and Compound III: 2-methyl-4,6-bis(p-N,N-dimethylaminostyryl)-s-triazine (NMe-2). NMe-1 and NEt-1 molecules belong to the D-π -A type with a one-dimensional charge-transfer character. NMe-1 crystallizes to centrosymmetric \(P\bar 1\) space group, while NEt-1 to non-centrosymmetric polar Cc space group with all of the molecular charge-transfer axes taking the same orientation. Under the irradiation of 1064 nm fundamental laser, NEt-1 powder crystals radiate a 2-order harmonic light with an intensity 46.8 times that of urea. The ∧ A typed NMe-2 molecule, which has a two-dimensional charge-transfer character, crystallizes to polar P21 space group. Its powder crystals exhibit a 2-order harmonic intensity 46.2 times that of urea. The quantum chemical calculations and tensor analyses have been carried out to reveal the dependence of the macro 2-order nonlinear optical (NLO) efficiency on the micro 2-order NLO coefficients (β) and on the crystalline packing styles.

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References

  1. Chemla, D. S., Zyss, J., eds., Nonlinear Optical Properties of Organic Molecules and Crystals, Vol. I, Orlando: Academic Press, 1987.

    Google Scholar 

  2. Kanis, D. R., Ratner, M. A., Marks T. J., Design and construction of molecular assemblies with large second-order optical nonlinearities, quantum chemical aspects, Chem. Rev., 1994, 94: 195–242.

    Article  CAS  Google Scholar 

  3. Verbiest, T., Houbrechts, S., Kauranen, M. et al., Second-order nonlinear optical materials: recent advances in chromophore design, J. Mater. Chem., 1997, 7(11): 2175–2189.

    Article  CAS  Google Scholar 

  4. Zyss, J., Nicoud, J. F., Coquillay, M., Chirality and hydrogen bonding in molecular crystals for phase-matched second- harmonic generation: N-(4-nitrophenyl)-(L)-prolinol (NPP), J. Chem. Phys., 1984, 81(9): 4160–4167.

    Article  CAS  Google Scholar 

  5. Tarn, W., Guerin, B., Calabrese, J. C. et al., 3-Methyl-4-methoxy-4′-nitrostilbene (MMONS): Crystal structure of a highly efficient material for second-harmonic generation, Chem. Phys. Lett., 1989, 154(2): 93–96.

    Article  Google Scholar 

  6. Luo, J. D., Hua, J. L., Qin, J. G. et al., The design of second-order nonlinear optical chromophores exhibiting blue-shifted absorption and large nonlinearities: The role of the combined conjugation bridge, Chem. Commun., 2001: 171–172.

  7. Ohkita, M., Suzuki, T., Nakatani, K. et al., Crystal engineering using very short and linear C(sp)-H...N hydrogen bonds: Formation of head-to-tail straight tapes and their assembly into nonlinear optical polar crystals, Chem. Commun., 2001: 1454- 455.

  8. Zyss, J., Ledoux, I., Bertault, M. et al., Dimethylaminocyan obiphenyl (DMACB): Anew optimized molecular crystal for quadratic nonlinear optics in the visible, Chem. Phys., 1991, 150: 125–135.

    Article  CAS  Google Scholar 

  9. Marder, S. R., Perry, J. W., Schaefer, W. P., Synthesis of organic salts with large second-order optical nonlinearities, Science, 1989, 245: 626–628.

    Article  CAS  Google Scholar 

  10. Li, Z. D., Huang, L. R., Su, G B. et al., Crystal structure of 4-bromo-4′-methoxyl-chalcone, J. Struct. Chem., 1992, 11(1): 1–4.

    Google Scholar 

  11. Zyss, J., Chemla, D. S., Nicoud, J. F., Demonstration of efficient nonlinear optical crystals with vanishing molecular dipole moment: Second-harmonic generation in 3-methyl-4-nitropyridine1-oxide, J. Chem. Phys., 1981, 74(9): 4800–4811.

    Article  CAS  Google Scholar 

  12. Fang, Q., Jiang, M. H., Qu, Z. et al., Nonlinear optical properties of DMIT derivatives, J. Mater. Chem., 1994, 4(7): 1041–1045.

    Article  CAS  Google Scholar 

  13. Zyss, J., Octupolar organic systems in quadratic nonlinear optics: Molecules and materials, Nonlinear Optics, 1991, 1: 3 - 18.

    CAS  Google Scholar 

  14. Cho, B. R., Park, S. B., Lee, S. J. et al., l,3,5-tricyano-2,4,6-tris(vinyl)benzene derivatives with large second-order nonlinear optical properties, J. Am. Chem. Soc., 2001, 123: 6421 -6422.

    Article  CAS  Google Scholar 

  15. Cui, Y. Z., Fang, Q., Lei, H. et al., Syntheses, structure and second-order nonlinear optical properties of octupolar compounds: 2,4,6-tri-substituted s-triazine, Chem. Phys. Lett., 2003, 377: 507–511.

    Article  CAS  Google Scholar 

  16. Oudar, J. L., Chemla, D. S., Hyperpolarizabilities of the nitroanilines and their relations to the excited state dipole moment, J. Chem. Phys., 1977, 66(6): 2664–2668.

    Article  CAS  Google Scholar 

  17. Kurtz, S. K., Perry, T. T., A powder technique for the evaluation of nonlinear optical materials, J. Appl. Phys., 1968, 39(8): 3798–3813.

    Article  CAS  Google Scholar 

  18. Willetts, A., Rice, J. E., Burland, D. M. et al., Problems in the comparison of theoretical and experimental hyperpolarizabilities, J. Chem. Phys., 1992, 97(10): 7590–7599.

    Article  CAS  Google Scholar 

  19. Frisch, M. J., Trucks, G W., Schlegel, H. B. et al., Gaussian 03, Revision B.5, Pittsburgh PA: Gaussian, Inc., 2003.

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Authors and Affiliations

  1. State Key Laboratory of Crystal Materials, Shandong University, 250100, Jinan, China

    Qi Fang, Gang Xue & Wentao Yu

  2. School of Information Science and Engineering, Shandong University, 250100, Jinan, China

    Hong Lei

  3. Department of Chemical Engineering, Light Industry College of Shandong, 250100, Jinan, China

    Yuezhi Cui

  4. Key Laboratory of Biomedical Photonics, Ministry of Education, Huazhong University of Science and Technology, 430074, Wuhan, China

    Zhenli Huang

Authors
  1. Qi Fang
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  2. Hong Lei
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  3. Yuezhi Cui
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  4. Zhenli Huang
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  5. Gang Xue
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  6. Wentao Yu
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Correspondence to Qi Fang.

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Fang, Q., Lei, H., Cui, Y. et al. Large second-order optical nonlinearities of s-triazine derivatives: View from micro molecules to macro crystals. Sc. China Ser. B-Chem. 48, 203–209 (2005). https://doi.org/10.1360/04yb0126

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