我們合成出以 N,N,-diphenylpyridine-2,6-dicarboxamide 為主要形成凝膠結
構並加入 pyrene 為修飾片段，並在 pyridine-2,6-dicarboxamide 的兩個醯胺氮原
子上與含碳氫長鏈苯基結合的單取代凝膠分子 DT79 與 1,6 雙取代凝膠分子
DT185。在形成凝膠能力的測試中發現 DT79 與 DT185 能在多種低極性有機
溶劑中形成凝膠，並且在 cyclohexane 具良好的形成凝膠能力。在稀薄溶液的吸
收與螢光光譜實驗中，我們發現 DT79 與 DT185 在 cyclohexane 同時具有聚
集與溶解狀態。我們以變溫吸收光譜、變溫螢光光譜及不同狀態下的吸收、螢光
光譜探討其分子間作用力及光物理變化，得知 DT79 與 DT185 會形成聚集及
分子間自組裝主要以 J-type 聚集形式進行；利用 1H NMR 了解凝膠分子形成凝
膠主要作用是以分子間的氫鍵與 π − π 作用力。透過 SEM 觀察，凝膠分子會
自組裝排列成纖維結構。

A series of supramolecular gelators, DT79 and DT185, based on pyrene with alkyl
chain pyridine-2,6-dicarboxamides has been synthesized. All gelators show excellent
gelation ability in many organic solvents. A variety of spectroscopic methods have
been applied to identify the intermolecular interactions upon gel formation and
explore the photophysical properties. In dilute solution absorption and fluorescence
spectroscopy experiments, we found that DT79 and DT185 in cyclohexane both
aggregation and dissolved state. The primary driving forces for the gel formation are
intermolecular hydrogen bonding, aromatic π − π, interactions. The supramolecular
aggregates in these organogels are considered to be the J-type aggregation. SEM
morphologies on the xerogels reveal that the gelators self-assembled into fibers.

摘要..I
Abstract .. II
謝誌..III
目錄..V
圖目錄..VII
表目錄..X
1. 緒論..1
1-1 凝膠的定義..1
1-2 凝膠的形成與分類..2
1-2-1 依來源分類..2
1-2-2 依介質分類..3
1-2-3 依其組成與交互作用力分類..3
1-3 小分子有機凝膠..4
1-4 小分子有機凝膠分類..6
1-4-1 Hydrocarbons LMOGs..6
1-4-2 Sugar-Based LMOGs ..8
1-4-3 Peptides LMOGs ...9
1-4-4 Metal complex LMOGs ..11
1-4-5 Two-component LMOGs ..14
1-4-6 Pyrene LMOGs ...16
1-5 研究動機..25
2. 實驗部分..26
2-1 分析儀器..26
2-1-1 核磁共振光譜儀..26
2-1-2 質譜分析..27
2-1-3 紫外-可見光吸收光譜儀..27
2-1-4 螢光光譜儀..28
2-1-5 場發射掃描式電子顯微鏡..28
2-1-6 螢光激態生命值測定光譜儀..29
2-2 實驗藥品..29
2-3 實驗合成..30
3. 結果與討論..36
3-1 凝膠分子DT79 及DT185 自組裝行為..36
3-1-1 不同溶劑形成凝膠能力測試..36
3-1-2 變溫核磁共振光譜實驗..39
3-2 凝膠分子DT79 及DT185 光物理性質..41
3-3 變溫UV-Vis 吸收光譜實驗、變溫螢光光譜實驗..55
3-4 稀薄溶液、凝膠、薄膜狀態吸收及螢光光譜實驗..61
3-4 分子聚集形貌研究..66
4. 結論..69
5. 實驗合成步驟..70
6. 參考資料..80
附錄..85

1. Terech, P.; Weiss, R. G. Chem. Rev. 1997, 97, 3133.
2. Sangeetha, N. M.; Maitra, U. Chem. Soc. Rev. 2005, 34, 821.
3. Weiss, R.G.; Terech, P.; eds. Molecular Gels. Materials with Self-Assembled
Fibrillar Networks, Springer, Dordrecht, The Netherlands, 2006.
4. Stupp, S. I. Nano Lett. 2010, 10, 4783.
5. Bardelang, D.; Zaman, M. B.; Moudrakovski, I. L.; Pawsey, S.; Margeson, J. C.;
Wang, D.; Wi, X.; Ripmeester, J. A.; Ratcliffe C. I.; Yu, K. Adv. Mater. 2008, 20,
4517.
6. Amabilino, D. B.; Puigmarti-Luis, J. Soft Matter. 2010, 6, 1605.
7. von Lipowitz, A. Liebigs Ann. Chem. Pharm. 1841, 38, 348.
8. Graham, T. Philos. Trans. R. Soc. London. 1861, 151.
9. D. Jordan Lloyd, in Colloid Chemistry, ed. J. Alexander, The Chemical Catalog
Co, New York, 1926, vol. 1, pp. 767.
10. Flory, P. J. Faraday Discuss. Chem. Soc. 1974, 57, 7.
11. Estroff , L. A. ; Hamilton, A. D. Chem. Rev. 2004, 104, 1201.
12. Yu, G.; Yan, X.; Han, C.; Huang F. Chem. Soc. Rev. 2013, 42, 6697.
13. Steed, J. W. Chem. Soc. Rev. 2010, 39, 3686.
14. Hench, L. L.; West, J. K. Chem. Rev. 1990, 90, 33.
15. Aharoni, S. M. in Synthesis, Characterization, and Theory of Polymeric Networks
and Gels, ed. S. M. Aharoni, Plenum, New York, 1992.
16. Zubarev, E. R.; Pralle, M. U.; Sone E. D.; Stupp, S. I. Adv. Mater. 2002, 14, 198.
17. de Loos, M. Hydrogen Bonded Low Molecular Weight Gelators
Structure-Property Relations, Ph.D. thesis, Universityof Groningen, 2005.
18. Atwood J. L.; Steed, J. W.; eds. Organic Nanostructures, 111, Wiley-VCH,
Weinheim, 2008.
19. Jonkheijm, P.; van der Schoot, P.; Schenning, A.; Meijer, E. W. Science. 2006,
313, 80.
20. Piepenbrock, M. O. M.; Lloyd, G. O.; Clarke, N.; Steed, J. W. Chem. Rev. 2010,
110, 1960.
21. Maity, G. C. J. Phys. Sci. 2007, 11, 156.
22. Abdallah, D. J.; Weiss, R. G. Langumir. 2000, 16, 352.
23. Abdallah, D. J.; Sirchio, S. A.; Weiss, R. G. Langumir. 2000, 16, 7558.
24. Menger, F. M.; Seredyuk, V. A.; Apkarian, R. P.; Wright, E. R. J. Am. Chem. Soc.
2002, 124, 12408.
25. Hafkamp, R. J. H.; Feiters, M. C.; Nolte, R. J. M. J. Org. Chem. 1999, 64, 412.
26. John, G.; Gung, J. H.; Masuda, M.; Shimizu, T. Langmuir. 2004, 20, 2060.
27. Gronwald, O.; Shinkai, S. Chem. Eur. J. 2001, 7, 4328.
28. Friggeri, A.; Gronwald, O.; van Bommel, K. J. C.; Shinkai, S.; Reinhoudt, D. N.
J. Am. Chem. Soc. 2002, 124, 10754.
29. Bhattacharya, S.; Acharya, S. N. G. Chem. Blank Mater. 1999, 11, 3504.
30. Mahler, A., Reches, M., Rechter, M., Cohen S. and E. Gazit, Adv. Mater. 2006,
18, 1365.
31. B.Adhikari, J.NandaandA.Banerjee, Chem. Eur. J. 2011, 17, 11488.
32. A. Heeres, C. van der Pol, M. Stuart, A. Friggeri, B. L. Feringa and J. van Esch,
J. Am. Chem. Soc. 2003, 125, 14252.
33. M. de Loos, J. H. van Esch, R. M. Kellogg and B. L. Feringa, Tetrahedron, 2007,
63, 7285.
34. Strassert, C. A.; Chien, C. H.; Lopez, M. D. G.; Kourkoulos, D.; Hertel, D.;
Meerholz, K.; Cola, L. D. Angew. Chem. Int. Ed. 2011, 50, 946.
35. de Hatten, X.; Bell, N.; Yufa, N.; Christmann, G.; Nitschke, J. R.
J. Am. Chem. Soc. 2011, 133, 3158.
36. Zhang, J. J.; Lu, W.; Sun, R. W. Y.; Che, C. M. Angew. Chem. Int. Ed. 2012, 51,
4882.
37. Zhang, S.; Yang, S. ; Lan, J.; Tang, Y.; Xue, Y.; You, J. J. Am. Chem. Soc. 2009,
131, 1689.
38. Beck, J. B.; Rowan, S. J. J. Am. Chem. Soc. 2003, 125, 13922.
39. Ishi-i, T.; Iguchi, R.; Snip, E.; Ikeda, M.; Shinkai, S. Langmuir. 2001, 17, 5825.
40. Ishi-i, T.; Jung, J. H.; Shinkai, S. J. Mater. Chem. 2000, 10, 2238.
41. Liu, J.; He, P.; Yan, J.; Fang, X.; Peng, J.; Liu, K.; Fang, Y. Adv. Mater. 2008, 20,
2508.
42. Chang, K. C.; Lin, J. L.; Shen, Y. T.; Hung, C. Y.; Chen, C. Y.; Sun, S. S.
Chem. Eur. J. 2012, 18, 1312.
43. Buerklea , L. E. and Rowan . S. J. Chem. Soc. Rev. 2012, 41, 6089.
44. Lehn, J. M.; Mascal, M.; Decian, A.; Fischer, J. J. Chem. Soc. Chem. Commun.
1990, 479.
45. Moffat, J. R. Chem. Commun. 2009, 316, 318.
46. Förster, T.; Kasper, K. Z. Electrochem. 1955, 59, 976.
47. Okamoto, A.; Kanatani, K.; Saito, I. J. Am. Chem. Soc. 2004, 126, 4820.
48. Jia, W. L.; McCormick, T.; Liu, Q.-D.; Fukutani, H.; Motala, M.; Wang, R.-Y.;
Tao, Y.; Wang, S. J. Mater. Chem. 2004, 14, 3344.
49. Percec, V.; Glodde, M.; Bera, T. K.; Miura, Y.; Shiyanovskaya, I.; Singer, K. D.;
Balagurusamy, V. S. K.; Heiney, P. A.; Schnell, I.; Rapp, A.; Spiess, H.-W.;
Hudson, S. D.; Duan, H. Nature. 2002, 419, 384.
50. Bernhardt, S.; Kastler, M.; Enkelmann, V.; Baumgarten, M.; Müllen, K. Chem.
Eur. J. 2006, 12, 6117.
51. Maeda, H.; Maeda, T.; Mizuno, K.; Fujimoto, K. Chem. Eur. J., 2006, 12, 824.
Diring, S.; Camerel, F.; Donnio, B.; Dintzer, T.; Toffanin, S.; Capelli, R.;
Muccini, M.; Ziessel, R. J. Am. Chem. Soc. 2009, 131, 18177.
52. Xu, X. D.; Zhang, J.; Yu, X.; Chen, L. j.; Wang, D. X.; Yi, T.; Li, F.; Yang, H. B.
Chem. Eur. J. 2012, 18, 16000.
53. Kamikawa, Y.; Kato, T. Langmuir. 2007, 23, 274.
54. Tsou, C. C.; Sun, S. S. Org. Lett. 2006, 8, 387.
55. Horváth, G.; Rusa, C.; Köntös, Z.; Gerencsér, J.; Huszthy, P. Synth. Commun.
1999, 3719.
56. Pryor, K. E.; Shipps, G. W.; Skyler, D. A.; Rebek, J. Tetrahedron. 1998, 54,
4107.
57. Das, K.; Nakade, H.; Penelle, J.; Rotello, V. M. Macromolecules. 2004, 37, 310.
58. Sharif, M., Reimann, S.; Wittler, K.; Knöpke, L. R.; Surkus, A. E.; Roth, C.;
Villinger, A.; Ludwig, R.; Langer, P. Eur. J. Org. Chem. 2011, 27, 5261.
59. Rivera, E.; Belletˆete, M.; Zhu, X. X.; Durocher, G.; Giasson, R. Polymer. 2002,
43, 5059.
60. Hissler, M.; Harriman, A.; Khatyr, A.; Ziessel, R. Chem. Eur. J. 1999, 5, 3366.
61. Leroy-Lhez, S.; Fages, F. Eur. J. Org. Chem. 2005, 13, 2684.
62. Ji, S.; Yang, J.; Yang, Q.; Liu, S.; Chen, M.; Zhao, J. J. Org. Chem. 2009, 74,
4855.
63. Brouwer, A. M. Pure Appl. Chem. 2011, 83, 2213.
64. 蔡孟學. 疏氟效應及鉑-鉑金屬作用力之超分子凝膠自組裝行為之研究. 國立
中央大學. 2013.
65. Yan, N.; Xu, Z.; Diehn, K. K.; Raghavan, S. R.; Fang, Y.; Weiss, R. G. Langmuir
2013, 29, 793.
66. Rajamalli, P.; Prasad, E. Soft Matter 2012, 8, 8896.
67. Yan, i.; Xu, Z.; Diehn, K. K.; Raghavan, S. R.; Fang, Y.; Weiss, R. G.
J. Am. Chem. Soc. 2013, 135, 8989.
68. Kimura, M.; Miki, N.; Suzuki, D.; Adachi, N.; Tatewaki, Y.; Shirai H. Langmuir
2009, 25, 776.
69. Mandal, D.; Kar, T.; Das, P. K. Chem. Eur. J. 2013, 19, 1.
70. Bhuniya , S.; Kim, B. H. Chem. Commun. 2006, 1842.
71. Moffat, J. R.; Smith, D. K. Chem. Commun. 2008, 2248.