Title

無鏈彎曲形分子之構形對液晶性質之影響及引入具立體障礙氟原子對形成扇葉構形對筒型液晶排列螺旋性之影響

Translated Titles

Influences of Sterically Congested Fluoro Substituents in Hexakis(pheneylethynyl)benzenes on the Helical Columnar Packing

DOI

10.6846/TKU.2011.00808

Authors

郭芷綺

Key Words

液晶 ; 彎曲型 ; 無鏈 ; 盤形 ; 掌性 ; 掌性放大 ; 螺旋 ; liquid crystal ; bent-rod ; chainfree ; discotic ; chiral induction ; chiral amplification ; helical swirl

PublicationName

淡江大學化學學系碩士班學位論文

Volume or Term/Year and Month of Publication

2011年

Academic Degree Category

碩士

Advisor

徐秀福

Content Language

英文

Chinese Abstract

本論文分別討論無鏈彎曲形分子之構形對液晶性質之影響及引入具立體障礙氟原子對形成扇葉構形對筒型液晶排列螺旋性之影響。第一部分分別以置換不同的末端官能基與改變其分子側臂的夾角,並佐以單晶結果,探討其無鏈彎曲形分子之構形對液晶性質之影響。第二部分設計單側臂具立體障礙氟原子之六側臂盤狀液晶分子,由氟原子數的增加所增加分子側鏈與分子中心核的平面扭轉角,以形成顯著的類風扇構形,使分子排列與推疊時更為緊密,同時提升了分子排列的次序性。無鏈彎曲形分子之構形對液晶性質之影響及引入具立體障礙氟原子對形成扇葉構形對筒型液晶排列螺旋性之影響。

English Abstract

The structure-property relationships of liquid crystalline behaviors have been well discussed in the past few decades. In general, the resulting intermolecular cohesion determines the fusion temperature of crystal and flexible chains lower the transition temperatures, thereby stabilizing the mesophases. Nevertheless, there are only a few example on the formation of liquid crystalline phases from mesogens without flexible chains. Herein, we investigated the effect of the molecular geometry, especially the dihedral angle and the dipole moment on liquid crystal formation of mesogenic compounds without flexible chains. A series of new bent-rod LCs without flexible chains were studied. Induced supramolecular chirality has been observed and reported in columnar LCs when the columns are twisted along the column axis to give helical structures. Hexaynylphenylbenzenes are prochiral due to the possible propeller-like geometry by rotation of sidearms. In this content, one or two lateral fluoro groups were incorporated ortho to ethynyl group onto on peripheral phenyl of hexaynylphenylbenzene. With unique combination of small size and high polarity, fluoro substituent can efficiently modify the mesogenic properties without significantly affecting the molecular geometry. In here, the sterics by the fluoro group(s) is to increase the dihedral angle of the F-attached phenyl and central phenyl to result in a more pronounced propeller geometry. The synthesized fluoro-containing compounds are expected to show higher ordering levels associated to helical disposition along the columns and more efficient chiral amplification is anticipated when these compounds are doped into non-chiral analogs.

Topic Category 基礎與應用科學 > 化學
理學院 > 化學學系碩士班
Reference
  1. 1. Collings, P. J.; Hird, M., Introdution to Liquid Crystals Chemistry and Physics. Taylor and Francis: London, 1997.
    連結:
  2. 5. Negredo, A.; Nacrro, F., Liq. Cryst. 2002, 29, 1-8.
    連結:
  3. 6. Ohta, K.; Shibuya, T.; Ando, M., J. Mater. Chem. 2006, 16, 3635-3639.
    連結:
  4. 7. Hird, M., Chem. Soc. Rev. 2007, 36, 2070-2095.
    連結:
  5. 8. Chandrasekhar, S., Liquid Crystals. 2nd ed.; Cambridge University Press: Cambridge, 1992.
    連結:
  6. 10. Reinitzer, F., Monatsh. Chem. 1888, 9, 421-441.
    連結:
  7. 12. Lehmann, O., Z. Phys. Chem. 1889, 4, 462-472.
    連結:
  8. 17. Niori, T., J. Mater. Chem. 1996, 6, 1231-1233.
    連結:
  9. 19. Paraskos, A. J.; Swager, T. M., Chem. Mater. 2002, 14, 4543-4549.
    連結:
  10. 21. Keith, C.; Amaranatha Reddy, R.; Baumeister, U.; Tschierske, C., J. Am. Chem. Soc. 2004, 126, 14312-14313.
    連結:
  11. 22. Balamurugan, S.; Kannan, P.; Chuang, M. T.; Wu, S. L., Ind. Eng. Chem. Res. 2010, 49, 7121-7128.
    連結:
  12. 25. Hsu, H. F.; Chien, S. J.; Chen, H. H.; Chen, C. H.; Huang, L. Y.; Kuo, C. H.; Chen, K. J.; Ong, C. W.; Wong, K. T., Liq. Cryst. 2005, 32, 683-689.
    連結:
  13. 26. Han, J.; Wang, Y. M.; Wang, X. G., Chin. J. Chem. 2006, 24, 1594-1598.
    連結:
  14. 27. Seed, A., Chem. Soc. Rev. 2007, 36, 2046-2069.
    連結:
  15. 29. Vorlander, D., Ber. Dtsch. Chem. Ges. 1910, 43, 3120-3135.
    連結:
  16. 1. Collings, P. J.; Hird, M., Introdution to Liquid Crystals Chemistry and Physics. Taylor and Francis: London, 1997.
    連結:
  17. 5. Negredo, A.; Nacrro, F., Liq. Cryst. 2002, 29, 1-8.
    連結:
  18. 6. Ohta, K.; Shibuya, T.; Ando, M., J. Mater. Chem. 2006, 16, 3635-3639.
    連結:
  19. 7. Hird, M., Chem. Soc. Rev. 2007, 36, 2070-2095.
    連結:
  20. 8. Chandrasekhar, S., Liquid Crystals. 2nd ed.; Cambridge University Press: Cambridge, 1992.
    連結:
  21. 10. Reinitzer, F., Monatsh. Chem. 1888, 9, 421-441.
    連結:
  22. 12. Lehmann, O., Z. Phys. Chem. 1889, 4, 462-472.
    連結:
  23. 17. Niori, T., J. Mater. Chem. 1996, 6, 1231-1233.
    連結:
  24. 19. Paraskos, A. J.; Swager, T. M., Chem. Mater. 2002, 14, 4543-4549.
    連結:
  25. 21. Keith, C.; Amaranatha Reddy, R.; Baumeister, U.; Tschierske, C., J. Am. Chem. Soc. 2004, 126, 14312-14313.
    連結:
  26. 22. Balamurugan, S.; Kannan, P.; Chuang, M. T.; Wu, S. L., Ind. Eng. Chem. Res. 2010, 49, 7121-7128.
    連結:
  27. 25. Hsu, H. F.; Chien, S. J.; Chen, H. H.; Chen, C. H.; Huang, L. Y.; Kuo, C. H.; Chen, K. J.; Ong, C. W.; Wong, K. T., Liq. Cryst. 2005, 32, 683-689.
    連結:
  28. 26. Han, J.; Wang, Y. M.; Wang, X. G., Chin. J. Chem. 2006, 24, 1594-1598.
    連結:
  29. 27. Seed, A., Chem. Soc. Rev. 2007, 36, 2046-2069.
    連結:
  30. 29. Vorlander, D., Ber. Dtsch. Chem. Ges. 1910, 43, 3120-3135.
    連結:
  31. 36. Han, J.; Zhang, F. Y.; Chen, Z.; Wang, J. Y.; Zhu, L. R.; Pang, M. L.; Meng, J. B., Liq. Cryst. 2008, 35, 1359-1365.
    連結:
  32. 46. Palmans, A. R. A.; Meijer, E. W., Angew. Chem. Int. Ed. 2007, 46, 8948-8968.
    連結:
  33. 47. Praefcke, K.; Kohne, B.; Singer, D., Angew. Chem. Int. Ed. 1990, 29, 177-179.
    連結:
  34. 49. Chien, S. C.; Chen, H. H.; Chen, H. C.; Yang, Y. L.; Hsu, H. F.; Shih, T. L.; Lee, J. J., Adv. Funct. Mater. 2007, 17, 1896-1902.
    連結:
  35. 50. Lee, S.-L.; Lin, H.-A.; Lin, Y.-H.; Chen, H.-H.; Liao, C.-T.; Lin, T.-L.; Chu, Y.-C.; Hsu, H.-F.; Chen, C.-h.; Lee, J.-J.; Hung, W.-Y.; Liu, Q.-Y.; Wu, C., Chem. Eur. J. 2011, 17, 792-799.
    連結:
  36. 54. Lin, H. A. Undergraduate, Tamkang University, Taiwan, 2005.
    連結:
  37. 57. Sonogashira, K.; Tohda, Y.; Hagihara, N., Tetrahedron Lett. 1975, 16, 4467-4470.
    連結:
  38. 58. Demus, D.; Richter, L., Texture of Liquid Crystals. Verlag Chemie: Weinheim, 1984.
    連結:
  39. 2. Gray, G. W., Thermotropic Liquid Crystals. Published on behalf of the Society of Chemical Industry by Wiley: New York, 1987.
  40. 3. Vorlander, D., Z. Phys. Chem. 1927, 126, 449-472.
  41. 4. Dingemans, T. J.; Murthy, N. S.; Samulski, E. T., J. Phy. Chem. B 2001, 105, 8845-8860.
  42. 9. Collings, P. J., Liquid Crystal: Nature's Dilicate Phase of Matter. Princeton University Press: New Jersey, 1990.
  43. 11. Dierking, I., Texture of Liquid Crystals. Wiley-VCH: Weinheim, 2003.
  44. 13. Friedel, G., Ann. Phys. 1992, 18, 272-283.
  45. 14. Zafiropoulos, N. A.; Choi, E. J.; Dingemans, T.; Lin, W.; Samulski, E. T., Chem. Mater. 2008, 20, 3821-3831.
  46. 15. Chandrasekhar, S.; Sadashiva, B. K.; Suresh, K. A., Pramana 1977, 9, 471-480.
  47. 16. Laschat, S.; Baro, A.; Steinke, N.; Giesselmann, F.; Hagele, C.; Scalia, G.; Judele, R.; Kapatsina, E.; Sauer, S.; Schreivogel, A.; Tosoni, M., Angew. Chem. Int.Ed. 2007, 46, 4832-4887.
  48. 18. Sekine, T.; Niori, T.; Watanabe, J.; Furukawa, T.; Choi, S. W.; Takezoe, H., J. Mater. Chem. 1997, 7, 1307-1309.
  49. 20. Gortz, V.; Southern, C.; Roberts, N. W.; Gleeson, H. F.; Goodby, J. W., Soft Matter 2009, 5, 463-471.
  50. 23. Yelamaggad, C. V.; Shashikala, I. S.; Liao, G.; Shankar Rao, D. S.; Prasad, S. K.; Li, Q.; Jakli, A., Chem. Mater. 2006, 18, 6100-6102.
  51. 24. Hsu, H.-F.; Kuo, C.-H.; Chen, C.-F.; Lin, Y.-H.; Huang, L.-Y.; Chen, C.-H.; Cheng, K.-C.; Chen, H.-H., Chem. Mater. 2004, 16, 2379-2385.
  52. 28. Kishikawa, K.; Harris, M. C.; Swager, T. M., Chem. Mater. 1999, 11, 867-871.
  53. 30. Barbera, J.; Rakitin, O. A.; Ros, M. B.; Torroba, T., Angew. Chem. Int. Ed. 1998, 37, 296-299.
  54. 31. Demus, D.; Sackmann, H.; Seibert, K., Wiss. Z. Univ. Halle. 1970, 19, 47-62.
  55. 32. Van Deun, R.; Ramaekers, J.; Nockemann, P.; Van Hecke, K.; Van Meervelt, L.; Binnemans, K., Eur. J. Inorg. Chem. 2005, 563-571.
  56. 2. Gray, G. W., Thermotropic Liquid Crystals. Published on behalf of the Society of Chemical Industry by Wiley: New York, 1987.
  57. 3. Vorlander, D., Z. Phys. Chem. 1927, 126, 449-472.
  58. 4. Dingemans, T. J.; Murthy, N. S.; Samulski, E. T., J. Phy. Chem. B 2001, 105, 8845-8860.
  59. 9. Collings, P. J., Liquid Crystal: Nature's Dilicate Phase of Matter. Princeton University Press: New Jersey, 1990.
  60. 11. Dierking, I., Texture of Liquid Crystals. Wiley-VCH: Weinheim, 2003.
  61. 13. Friedel, G., Ann. Phys. 1992, 18, 272-283.
  62. 14. Zafiropoulos, N. A.; Choi, E. J.; Dingemans, T.; Lin, W.; Samulski, E. T., Chem. Mater. 2008, 20, 3821-3831.
  63. 15. Chandrasekhar, S.; Sadashiva, B. K.; Suresh, K. A., Pramana 1977, 9, 471-480.
  64. 16. Laschat, S.; Baro, A.; Steinke, N.; Giesselmann, F.; Hagele, C.; Scalia, G.; Judele, R.; Kapatsina, E.; Sauer, S.; Schreivogel, A.; Tosoni, M., Angew. Chem. Int.Ed. 2007, 46, 4832-4887.
  65. 18. Sekine, T.; Niori, T.; Watanabe, J.; Furukawa, T.; Choi, S. W.; Takezoe, H., J. Mater. Chem. 1997, 7, 1307-1309.
  66. 20. Gortz, V.; Southern, C.; Roberts, N. W.; Gleeson, H. F.; Goodby, J. W., Soft Matter 2009, 5, 463-471.
  67. 23. Yelamaggad, C. V.; Shashikala, I. S.; Liao, G.; Shankar Rao, D. S.; Prasad, S. K.; Li, Q.; Jakli, A., Chem. Mater. 2006, 18, 6100-6102.
  68. 24. Hsu, H.-F.; Kuo, C.-H.; Chen, C.-F.; Lin, Y.-H.; Huang, L.-Y.; Chen, C.-H.; Cheng, K.-C.; Chen, H.-H., Chem. Mater. 2004, 16, 2379-2385.
  69. 28. Kishikawa, K.; Harris, M. C.; Swager, T. M., Chem. Mater. 1999, 11, 867-871.
  70. 30. Barbera, J.; Rakitin, O. A.; Ros, M. B.; Torroba, T., Angew. Chem. Int. Ed. 1998, 37, 296-299.
  71. 31. Demus, D.; Sackmann, H.; Seibert, K., Wiss. Z. Univ. Halle. 1970, 19, 47-62.
  72. 32. Van Deun, R.; Ramaekers, J.; Nockemann, P.; Van Hecke, K.; Van Meervelt, L.; Binnemans, K., Eur. J. Inorg. Chem. 2005, 563-571.
  73. 33. Irvine, P. A.; Wu, D. C.; Flory, P. J., Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases 1984, 80, 1795-1806.
  74. 34. Flory, P. J.; Irvine, P. A., Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases 1984, 80, 1807-1819.
  75. 35. Irvine, P. A.; Flory, P. J., Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases 1984, 80, 1821-1830.
  76. 37. Kuiper, S.; Jager, W. F.; Dingemans, T. J.; Picken, S. J., Liq. Cryst. 2009, 36, 389-396.
  77. 38. Chang, A. S. Master, Tamkang Unversity, Taiwan, 2005.
  78. 39. Hung, L. C. Liquid Crystals from Various Geometrical Assemblies of Bent Thiophene-Containing Moieties. Master Thesis, Tamkang University, Taiwan, 2007.
  79. 40. Amabilino, D. B.; Veciana, J., Top. Curr. Chem. 2006, 265, 253-302.
  80. 41. Vera, F.; Luis Serrano, J.; Sierra, T., Chem. Soc. Rev. 2009, 38, 781-796.
  81. 42. Boden, N.; Bushby, R. J.; Cammidge, A. N.; Duckworth, S.; Headdock, G., J. Mater. Chem. 1997, 7, 601-605.
  82. 43. Praefcke, K.; Singer, D.; Eckert, A., Liq. Cryst. 1994, 16, 53-65.
  83. 44. Praefcke, K.; Singer, D.; Usol'tseva, N.; Gudogan, B., Liq. Cryst. 1994, 16, 617-623.
  84. 45. Levelut, A. M.; Oswald, P.; Ghanem, A.; Malthete, J., J. Phy. 1984, 45, 745-754.
  85. 48. Sakajiri, K.; Sugisaki, T.; Moriya, K., Chem. Comm. 2008, 3447-3449.
  86. 51. Yeh, Y. H. Master, Tamkang University, Taiwan, 2010.
  87. 52. Chan, Y. H. Synthesis and Supramolecular Packing Patterns of Chiral Discs and Disc Dimers in Liquid Crystalline States. Master Thesis, Tamkang University, Taiwan, 2010.
  88. 53. Kumar, S.; Varshney, S. K., Angew. Chem. Int. Ed. 2000, 39, 3140-3142.
  89. 55. Tsao, S. W. Induction of Higher Intermolecular Packing by Introduction of Fluoro Groups onto Discotic Nematogens. Master Thesis, Tamkang University, Taiwan, 2008.
  90. 56. G. M. Sheldrick, SHELX 97, PC Version, University of Gottingen, 1997.
  91. 59. Liao, C.-T. Master, Tamkang, 2007.