Article
  • Thermotropic Liquid Crystalline and Photochemical Phase Transition Behavior of Octa[8-{4-(4'-cyanophenylazo)phenoxy}]octyl and Octa[8-{4-(4'-cyanophenylazo) phenoxycarbonyl}]heptanoated Disaccharides
  • Kim HG, Jung SY, Jeong HS, Ma YD
  • 옥타[8-{4-(4'-시아노페닐아조)펜옥시}]옥틸 그리고 옥타[8-{4-(4'-시아노페닐아조) 펜옥시카보닐}]헵타노화 이당류의 열방성 액정과 광화학적 상전이 거동
  • 김효갑, 정승용, 정희성, 마영대
Abstract
Octa[8-{4-(4'-cyanophenylazo)phenoxy}]octyl and octa[8-{4-(4'-cyanophenylazo)phenoxycarbonyl}]heptanoated disaccharide derivatives were synthesized by reacting cellobiose, maltose, and lactose with 1-{4-(4'-cyanophenylazo) phenoxy}octylbromide or 1-{4-(4'-cyanophenylazo)phenoxycarbonyl}]heptanoyl chloride, and their thermotropic liquid crystalline and photochemical phase transition behavior were investigated. All the {(cyanophenylazo)phenoxy}octyl disaccharide ethers (CADETs) formed monotropic nematic (N) phases, whereas all the {(cyanophenylazo)phenoxycarbonyl}heptanoated disaccharide esters (CADESs) exhibited enantiotropic N phases. Compared with CADETs, CADESs showed higher isotropic (I)-to-N phase transition temperatures. Photoirradiation of the disaccharide derivatives in a glass cell or in a cell with a rubbed polyimide (PI) alignment layer at a N phase resulted in disappearance of the N phase due to trans-cis photoisomerization of azobenzene, and the initial N phase was recovered when the irradiated sample was kept in the dark because of cis-trans thermal isomerization and reorientation of trans-azobenzenes. The rates of the photochemical N-I and the thermal I-N phase transition of disaccharide derivatives in a cell with a rubbed PI alignment layer were faster than those in a glass cell, and were significantly different from those observed for the monomesogenic compounds containing cyanoazobenzene and the 4-{4'-(cyanophenylazo)phenoxy}octyl glucose and cellulose ethers. The results were discussed in terms of difference in cooperative motion of azobenzene groups due to the flexibility of the main chain, the number of mesogenic units per repeating units, and the distance between the azobenzene groups.

셀로비오스, 말토오스 그리고 락토오스를 1-{4-(4'-시아노페닐아조)펜옥시}옥틸브롬 혹은 1-{4-(4'-시아노페닐아조)펜옥시카보닐}헵타노일 클로라이드와 반응시켜 옥타[8-{4-(4'-시아노페닐아조)펜옥시}]옥틸 그리고 옥타[8-{4-(4'-시아노페닐아조)펜옥시카보닐}]헵타노화 이당류 유도체들을 합성함과 동시에 이들의 열방성 액정과 광화학적 상전이 거동을 검토하였다. 모든 {(시아노페닐아조)펜옥시}옥틸 이당류 에테르들(CADETs)은 단방성 네마틱(N) 상들을 형성하는 반면 모든 {(시아노페닐아조)펜옥시카보닐}헵타노화 이당류 에스터들(CADESs)은 양방성 N 상들을 형성하였다. CADETs에 비해, CADESs는 높은 액체(I) 상에서 N 상으로의 전이 온도들을 나타냈다. 유리 셀 혹은 러빙된 폴리이미드(PI) 배향막을 지닌 셀 중에서 N 상을 형성하고 있는 이당류 유도체에 광을 조사시킬 경우, 아조벤젠기의 trans-cis 이성화에 의해 N 상은 I 상으로 변하였다. 한편, 광 조사시켜 얻은 시료를 광을 차단한 상태로 방치할 경우 열에 의한 cis-trans 이성화와 trans 아조벤젠기들의 재배열로 인하여 I 상은 최초의 N 상으로 변하였다. 유리 셀의 경우에 비해 러빙된 PI 배향막을 지닌 셀의 경우가 이당류 유도체들의 광화학적 N-I 그리고 열적 I-N 상전이 속도들은 빠르며 시아노아조벤젠기를 지닌 monomesogenic 화합물들 그리고 4-{4'-(시아노페닐아조)펜옥시}옥틸 글루코오스 그리고 셀룰로오스 에테르들에 대해 관찰되는 결과들에 비해 현저히 달랐다. 이러한 결과를 주사슬의 유연성, 반복단위당에 도입된 메소겐기들의 수 그리고 아조벤젠기들간의 거리에 기인한 아조벤젠기들의 협동효과의 차이의 견지에서 검토하였다.

Keywords: disaccharide; cyanoazobenzene; nematic phase; ester and ether linkage; photochemical; thermal phase transition.

References
  • 1. Goodby JW, Liq. Cryst., 24, 35 (1998)
  •  
  • 2. Dumoulin F, Lafont D, Boullanger P, Mackenzie G, Mehl GH, Goodby JW, J. Am. Chem. Soc., 124(46), 13737 (2002)
  •  
  • 3. Fukuda T, Tsujii Y, Miyamoto T, Macromol. Symp., 99, 257 (1995)
  •  
  • 4. Cammidge AN, Bushby RJ“Synthesis and Structural Features”, in Handbook of Liquid Crystals, Demus D, Goodby J, Gray GW, Spiess HW, Vill V, Editors, Wiley-VCH, Weinheim-New York, Vol 2B, Chap VII, 693 (1998)
  •  
  • 5. Goodby JW, Saez IM, Cowling SJ, Gortz V, Draper M, Hall AW, Sia S, Cosquer G, Lee SE, Raynes EP, Angew.Chem. Int. Ed., 47, 2754 (2008)
  •  
  • 6. Donaldson T, Staesche H, Lu ZB, Henderson PA, Achard MF, Imrie CT, Liq. Cryst., 37, 1097 (2010)
  •  
  • 7. Jeong SY, Ma YD, Polym.(Korea), 31(1), 58 (2007)
  •  
  • 8. Jeong SY, Ma YD, J. Korean Ind. Eng. Chem., 18(5), 475 (2007)
  •  
  • 9. Kim JH, Ma YD, J. Korean Ind. Eng. Chem., 15(1), 113 (2004)
  •  
  • 10. Jeong SY, Ma YD, Polym.(Korea), 32(3), 230 (2008)
  •  
  • 11. Takada A, Fukuda T, Miyamoto T, Watanabe J, Cell.Chem. Technol., 24, 693 (1990)
  •  
  • 12. Jeong SY, Kim IS, Ma YD, J. Korean Ind. Eng. Chem., 20(6), 603 (2009)
  •  
  • 13. Goodby JW, Mol. Cryst. Liq. Cryst., 110, 205 (1984)
  •  
  • 14. Laurent N, Lafont D, Dumoulin F, Boullanger P, Mackenzie G, Kouwer PHJ, Goodby JW, J. Am. Chem. Soc., 125(50), 15499 (2003)
  •  
  • 15. Harwood SM, Toyne KJ, Goodby JW, Liq. Cryst., 27, 443 (2000)
  •  
  • 16. Yelamaggad CV, Shanker G, Hiremath US, Krishna S, Prasad SK, J. Mater. Chem., 18, 2927 (2008)
  •  
  • 17. Emoto A, Uchida E, Fukuda T, Polymer., 4, 150 (2012)
  •  
  • 18. Yu HF, Ikeda T, Adv. Mater., 23(19), 2149 (2011)
  •  
  • 19. Tamaoki N, Kamei T, J. Photochem. Photobiol. C:Photochem. Rev., 11, 47 (2010)
  •  
  • 20. Shibaev V, Borovsky A, Boike N, Prog. Polym. Sci., 28, 729 (2003)
  •  
  • 21. Kurihara S, Iwamoto K, Nonaka T, J. Chem. Soc. Chem. Commun., 2195 (1995)
  •  
  • 22. Kurihara S, Iwamoto K, Nonaka T, Polymer, 39(15), 3565 (1998)
  •  
  • 23. Jeong SY, Son HM, Ma YD, Polym.(Korea), 34(2), 116 (2010)
  •  
  • 24. Jeong SY, Lee JY, Ma YD, Polym.(Korea), 33(4), 297 (2009)
  •  
  • 25. Jeong SY, Ma YD, J. Korean Ind. Eng. Chem., 19(5), 504 (2008)
  •  
  • 26. Sung JH, Hirano S, Tsutsumi O, Kanazawa A, Shiono T, Ikeda T, Chem. Mater., 14, 385 (2002)
  •  
  • 27. Jeong SY, Ma YD, Chemical Materials(Dankook University)., 4, 19 (2007)
  •  
  • 28. Gray GW, “Liquid Crystals and Molecular Structure-Nematics and Cholesterics”, in The Molecular Physics of Liquid Crystals, Luckhurst GR, Gray GW, Editors, Academic Press Inc., London, Chap 1, 1 (1979)
  •  
  • 29. Collings PJ, Hird M“Calamitic Liquid Crystals-Nematic and Smectic Mesophases”, in Introduction to Liquid Crystals, Gray GW, Goodby JW, Fukuda A, Editors, Taylor and Francis Ltd., London, Chap 3, 43 (1997)
  •  
  • 30. Jeong SY, Jeong JH, Ma YD, Tsujii Y, Polym.(Korea), 25(2), 279 (2001)
  •  
  • 31. Jeong SY, Ma YD, Polym.(Korea), 31(1), 37 (2007)
  •  
  • 32. Jeong SY, Ma YD, Polym.(Korea), 30(4), 338 (2006)
  •  
  • 33. Cha SW, Jin JI, Kim DC, Zin WC, Macromolecules, 34(15), 5342 (2001)
  •  
  • 34. Brehmer L, “Ultrathin Films for Sensors and Molecular Electronics”, in Polymer Sensors and Actuators, Osada Y, DeRossi DE, Editors, Springer-Verlag, Berlin, Chap 2, 15 (2000)
  •  
  • 35. Yager KG, Barrett CJ“Azobenzene Polymers for Photonic Applications”, in Smart Light-Responsive Materials: Azobenzene-Containing Polymers and Liquid Crystals, Zhao Y, Ikeda T, Editors, John Wiley & Son, Inc., Chap 1, 1 (2009)
  •  
  • 36. Liu JH, Hsieh CD, J. Appl. Polym. Sci., 99(5), 2443 (2006)
  •  
  • 37. Wu YL, Zhang QJ, Kanazawa A, Shiono T, Ikeda T, Nagase Y, Macromolecules, 32(12), 3951 (1999)
  •  
  • 38. Xia T, Li C, Yue Z, Macromolecules, 37(9), 3101 (2004)
  •  
  • 39. Ikeda T, Horiuchi S, Karanjit DB, Kurihara S, Tazuke S, Macromolecules., 23, 42 (1990)
  •  
  • 40. Ivanov S, Yakovlev I, Kostromin S, Shibaev V, Lasker L, Stumpe J, Kreysig D, Macromol. Chem. Rapid. Commun., 12, 709 (1991)
  •  
  • 41. Wu YL, Demachi Y, Tsutsumi O, Kanazawa A, Shiono T, Ikeda T, Macromolecules, 31(2), 349 (1998)
  •  
  • 42. Hasegawa M“Rubbing Technologies: Mechanisms and Applications”, in Alignment Technologies and Applications of Liquid Crystal Devices, Takatoh K, Hasegawa M, Koden M, Itoh N, Hasegawa R, Sakamoto M, Editors, Tayler & Francis, London and New York, Chap 2, 7 (2005)
  •  
  • 43. Lee M, Shin MY, Kim SH, Song K, Polym.(Korea), 35(5), 493 (2011)
  •  
  • 44. Sun Z, Qin A, Chen Z, Wang Y, Liq. Cryst., 37, 345 (2010)
  •  
  • 45. Natansohn A, Rochon P, Meng XS, Barrett C, Buffeteau T, Bonenfant S, Pezolet M, Macromolecules, 31(4), 1155 (1998)
  •  
  • 46. Wu YL, Demachi Y, Tsutsumi O, Kanazawa A, Shiono T, Ikeda T, Macromolecules, 31(4), 1104 (1998)
  •  
  • 47. Wu YL, Mamiya J, Kanazawa A, Shiono T, Ikeda T, Zhang QJ, Macromolecules, 32(26), 8829 (1999)
  •  
  • 48. Fisher T, Lasker L, Czapla S, Rubner J, Stumpe J, Mol.Cryst. Liq. Cryst., 298, 213 (1997)
  •  
  • 49. Tsutsumi O, Kitsunai T, Kanazawa A, Shiono T, Ikeda T, Macromolecules, 31(2), 355 (1998)
  •  
  • 50. Sasaki T, Ikeda T, Ichimura K, Macromolecules., 26, 151 (1993)
  •  
  • 51. Bobrovsky A, Boiko N, Shibaev VP, J. Mater. Chem., 10, 1075 (2000)
  •  
  • 52. Bobrovsky AY, Boiko NI, Shibaev VP, Springer J, Liq.Cryst., 28, 919 (2001)
  •  
  • 53. Sin SL, Gan LH, Hu X, Tam KC, Gan YY, Macromolecules, 38(9), 3943 (2005)
  •  
  • 54. Kumar SK, Hong JD, Lim CK, Park SY, Macromolecules, 39(9), 3217 (2006)
  •  
  • 55. Bobrovsky AY, Pakhomov AA, Zhu XM, Boiko NI, Shibaev VP, Stumpe J, J. Phys. Chem. B, 106(3), 540 (2002)
  •  
  • 56. Yang SZ, Jacob MM, Li L, Cholli AL, Kumar J, Tripathy SK, Macromolecules, 34(26), 9193 (2001)
  •  
  • 57. Tsutsumi O, Shiono T, Ikeda T, Galli G, J. Phys. Chem. B, 101(8), 1332 (1997)
  •  
  • Polymer(Korea) 폴리머
  • Frequency : Bimonthly(odd)
    ISSN 0379-153X(Print)
    ISSN 2234-8077(Online)
    Abbr. Polym. Korea
  • 2023 Impact Factor : 0.4
  • Indexed in SCIE

This Article

  • 2012; 36(6): 776-788

    Published online Nov 25, 2012

  • Received on Jun 27, 2012
  • Accepted on Aug 13, 2012