Functionalized polyolefinic nonlinear optic chromophores incorporating the 1,3-dithiol-2-ylidene moiety as the electron-donating part

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T. T. Nguyen, M. Sallé, J. Delaunay, A. Riou, P. Richomme, J. M. Raimundo, A. Gorgues, I. Ledoux, C. Dhenaut, J. Zyss, J. Orduna and J. Garín


Abstract

The synthesis of a series of push-pull systems [donor (D)–acceptor (A)], associating the 1,3-dithiol-2-ylidene moiety (D) to various (A) fragments through polyolefinic linkages of various lengths, is described. Design optimization of these NLO phores isvia systematic determination of the molecular first hyperpolarizabilities beta; by the EFISH method. Selected compounds of this series, displaying the highest beta; values, are then chemically functionalized in order to promote their covalent grafting to polymeric backbones.


References

  1. (a) Nonlinear Optical Properties of Organic Molecules and Crystals, ed. D. S. Chemla and J. Zyss, Academic Press, Orlando, 1987 Search PubMed; (b) Molecular Nonlinear Optics: Materials, Physics and Devices, ed. J. Zyss, Academic Press, Boston, 1994 Search PubMed; (c) Nonlinear Optics of Organic Molecules and Polymers, ed. H. S. Nalwa and S. Miyata, CRC Press, 1994 Search PubMed; (d) Introduction to Nonlinear Optical Effects in Molecules and Polymers, ed. N. Prasad and D. J. Williams, Wiley, New York, 1991 Search PubMed; (e) L. R. Dalton, A. W. Harper, R. Ghosn, W. H. Steier, M. Ziari, H. Fetterman, Y. Shi, R. V. Mustacich, K. Y. Jen and K. J. Shea, Chem. Mater., 1995, 7, 1060 CrossRef CAS.
  2. For a review about tetrathiafulvalene chemistry: J. Garin, Adv. Heterocyclo Chem., 1995, 62, 249 Search PubMed.
  3. See for instance: (a) H. E. Katz, K. D. Singer, J. E. Sohn, C. W. Dirk, L. A. King and H. M. Gordon, J. Am. Chem. Soc., 1987, 109, 6561 CrossRef CAS; (b) M. Blanchard-Desce, I. Ledoux, J. M. Lehn, J. Malthête and J. Zyss, J. Chem. Soc., Chem. Commun., 1988, 737 RSC; (c) M. Barzoukas, M. Blanchard, D. Josse, J. M. Lehn and J. Zyss, Chem. Phys., 1989, 133, 323 CrossRef CAS; (d) M. Blanchard-Desce, J. M. Lehn, M. Barzoukas, I. Ledoux and J. Zyss, Chem. Phys., 1994, 181, 281 CrossRef CAS; (e) A. K. Y. Jen, V. P. Rao, K. J. Drost, K. Y. Wong and M. P. Cava, J. Chem. Soc., Chem. Commun., 1994, 2057 RSC; (f) D. Lorcy, A. Robert, S. Triki, L. Ouahab and P. Robin, Tetrahedron Lett., 1994, 33, 7341 CrossRef CAS.
  4. T. T. Nguyen, Y. Gouriou, M. Sallé, P. Frère, M. Jubault, A. Gorgues, L. Toupet and A. Riou, Bull. Soc. Chim. Fr., 1996, 133, 301 CAS.
  5. Crystal data for compound 8a: C15H18O2S2, M= 294.43, triclinic, P1, Z= 2, a= 8.395(3), b= 9.830(4), c= 10.909(4)Å, α= 114.09(2), β= 99.99(3), γ= 96.42(3), V= 792.5(6)Å3, λ= 0.71073 Å. Data collection was carried out by the zig-zag ω/2θ scan technique (2 < θ < 25°) on an Enraf Nonius CAD4 diffractometer. Conditions of measurements were tmax= 40 s, range h, k, l[h(0, 10); k( 12, 12); l( 13, 13)]. Intensity control reflections were measured every 2 h without appreciable decay (0.15%). A total of 3098 independent reflections were collected from which 1153 corresponded to I > 3σ(I). Structure refinement: after Lorentz polarisation corrections, the structure was solved by direct methods using the general tangent phasing procedure (GENTAN), which revealed all the non-hydrogen atoms. After anisotropic refinement of S, O and C atoms, the coordinates of the H atoms were generated from the molecular geometry. The whole structure was refined by full-matrix least-squares techniques (refinement on F, x, y, z, Uij for S, O and C atoms, x, y, z, and U fixed for H atoms). 172 variables for 1153 observations, with the resulting R= 0.073, Rw= 0.078. All the calculations were performed using the XTAL 3.2 package.
  6. (a) D. N. Beratan, ACS Symp. Ser., 1991, 455, 89 CAS; (b) S. R. Marder, C. B. Gorman, L. T. Cheng and B. G. Tiemann, Proc. SPIE, 1993, 1775, 19 Search PubMed.
  7. S. R. Marder, C. B. Gorman, B. G. Tiemann and L. Cheng, J. Am. Chem. Soc., 1993, 115, 3006 CrossRef CAS.
  8. Crystal data for compound 12: C20H14S3N4, M= 406.55, monoclinic, P21/c, Z= 4, a= 10.856(2), b= 12.447(3), c= 14.995(13)Å, β= 99.69(3)°, V= 1997(2)Å3, λ= 0.71073 Å. Data collection was carried out by the zig-zag ω/2θ scan technique (2 < θ < 30°)on an Enraf Nonius Mach III diffractometer. Conditions of measurements were tmax= 40 s, range h, k, l[h(0, 15); k(0, 17); l( 21, 21)]. Intensity controls without appreciable decay (0.2%) gave 3801 reflections from which 2069 were independent with I > 3σ(I). Structure refinement: after Lorentz and polarisation corrections, the structure was solved by direct methods (SIR) which revealed all the non-hydrogen atoms. After anisotropic refinement of all the non-hydrogen atoms, the coordinates of the H atoms were determined from the HYDRO program. The whole structure was refined by full-matrix least-squares techniques (use of F magnitude; Uij for C, S and N atoms, x, y, z and B fixed for H); 244 variables for 2069 observations, weighting ω= 1/σ(F0)2=[σ2(I)+(0.04 F02)2]–1/2 with the resulting R= 0.048, Rw= 0.062. All the calculations were performed using the MOLEN package. Full Crystallographic details, excluding structure factors, have been deposited at the Cambridge Crystallographic Data Centre (CCDC). See Information for Authors, J. Mater. Chem., 1998, Issue 1. Any request to the CCDC for this material should quote the full literature citation and the reference number 1145/91 Search PubMed.
  9. J. L. Oudar, J. Chem. Phys., 1977, 67, 446 CrossRef CAS.
  10. For methacrylate NLO active polymers, see for instance: (a) C. Xu, B. Wu, O. Todorova and L. R. Dalton, Macromolecules, 1993, 26, 5303 CrossRef CAS; (b) J. Y. Lee and H. J. Lee, Polym. Bull., 1997, 38, 265 CrossRef CAS; (c) D. W. Kim, S. Hong, S. Y. Park and N. Kim, Bull. Korean Chem. Soc., 1997, 18, 198 CAS.
  11. (a) V. Y. Khodorkovsky, J. Y. Becker and J. Y. Bernstein, Synthesis, 1992, 1071 CrossRef; (b) J. S. Zambounis and C. W. Mayer, Tetrahedron Lett., 1991, 32, 2737 CrossRef CAS.
  12. (a) T. K. Hansen, T. Jorgensen, F. Jensen, P. H. Thygesen, K. Christiansen, M. B. Hursthouse, M. E. Harman, M. A. Malik, B. Girmay, A. E. Underhill, M. Begtrup, J. D. Kilburn, K. Belmore, P. Roepstorff and J. Becher, J. Org. Chem., 1993, 58, 1359 CrossRef CAS; (b) A. J. Moore and M. R. Bryce, J. Chem. Soc., Chem. Commun., 1991, 1639 Search PubMed.
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