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研究生： 黃民揚
Min-Yang Huang
論文名稱： 蒽分子衍生物修飾矽倍半氧寡聚物之合成鑑定與性質探討
Synthesis and Property of Polyhedral Oligomeric Silsesquioxanes Modified with Anthracene Derivatives
指導教授： 劉陵崗
Ling-Kang Liu
朱瑾
Jinn Chu
口試委員: 周大新
Ta-Hsin chou
張大釗
Ta-Chao Chang
學位類別： 碩士
Master
系所名稱： 應用科技學院 - 應用科技研究所
Graduate Institute of Applied Science and Technology
論文出版年： 2010
畢業學年度： 98
語文別： 中文
論文頁數： 98
中文關鍵詞： 八乙烯基八矽十二氧 、矽倍半氧寡聚物 、能量上轉移
外文關鍵詞： octavinylsilsesquioxane (OVS), POSS, upconversio
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    • 本研究，針對多面體矽倍半氧寡聚物(Polyhedral Oligomeric Silsesquioxane, POSS)之性質加以探討。合成分為三個部分嘗試，首先利用寡聚物八乙烯基八矽十二氧(OVS)進行Friedel-Crafts 反應，再進行溴化反應。第二部分將OVS與溴化合物行氫矽加成反應。最後OVS與含溴之蒽衍生物以Heck 反應相結合，合成了三種含有蒽衍生物之立方體矽倍半氧寡聚物與三種接上丙烯酸甲酯（MA）的蒽衍生物。
    各項產物均藉由1H NMR檢測。含有矽倍半氧寡聚物POSS的產物則以29Si NMR檢測，結果符合文獻之歸類數值。並利用FT-IR光譜在1100cm-1附近是否有吸收峰，確認化合物中矽氧鍵存在。
    將Heck 反應後的六種蒽衍生物作為能量上轉移中的發射團，並以不同濃度甲基藍作為光敏劑，及不同甲基藍對蒽衍生物發射團莫耳比例混合，找尋螢光光譜下之最佳化條件，觀測能量上轉移的情形。

    In this study, the polyhedral oligomeric silsesquioxanes (POSS) were synthesized and characterized. The synthesis in this study was divided into three parts. The first part of synthesis was the modification of octavinylsilsesquioxane (OVS) by Fridel-Crafts reaction, with further bromination. The second part was the OVS hydrosilylation with bromine containing compounds. The last part was the coupling of OVS and brominated derivatives by Heck reaction to obtain three anthracene derivatives, and three related methyl acrylate-anthracene derivatives.
    The products were assigned with 1H NMR spectroscopy. The products containing POSS were also identified detected by 29Si NMR spectroscopy. The results were consistent to that of the literature values. In the FT-IR spectra, there were also the 1100cm-1 absorption bonds,
    confirming that the complexes have silicon-oxygen bonds in structure.
    The above six anthracene derivatives prepared by Heck reaction were utilized as emitters in an upconversion study, with methylene blue as a sensitizer, varying in concentrations. The best conditions were obtained by the fluorescence spectra with different molar ratios in
    mixtures.

    章節目錄 中文摘要………………………………………………………………….i 英文摘要………………………...……………………………………….ii 謝誌……………………...………………………………..……..………iii 目錄………………………………………………………………......….iv 圖目錄……………………………………………………….....……….vii 表目錄………………………………..……………...………...……….xiii 第一章 緒論……………………………………………………...……...1 1.1 有機無機奈米複合材料-矽倍半氧寡聚物(Polyhedral Oligomeric Silsesquioxane, POSS) …………………………………………………..1 1.1.1 原子團簇………………………………………………………1 1.1.2 奈米微粒………………………………………………………1 1.1.3 奈米粒子薄膜…………………………………………………2 1.1.4 奈米固體 ……………………………………………………..2 1.1.5 複合材料 ……………………………………………………..3 1.2. 矽倍半氧寡聚物……………………………………………………5 1.2.1 矽倍半氧寡聚物的種類與定義……………………………..7 1.2.2 矽倍半氧寡聚物的結構……………………………………..9 1.2.3 矽倍半氧寡聚物的合成方式………………………..……..12 1.2.4 矽倍半氧寡聚物的常見衍生物及其合成方式………..…..14 1.3螢光理論……………………………………………………..……...17 1.3.1 單重態與三重態…………………..………………..……..18 1.3.2 態能階圖…………………………………………..……....19 1.4 能量上轉移……………………………………………….……….23 1.4.1能量上轉移的機制…………………………………….……23 1.4.2能量上轉的條件……………………………….…….……...25 1.4.3能量上轉移的參考文獻…………………………….………26 第二章 實驗部份……………………………………………..……......29 2.1 研究動機…………………………………………………..……….29 2.2 藥品部分…………………………………………………………...29 2.3 儀器部分……………………………………………..…….……...33 2.4 實驗合成步驟 ………………………………………….…….......36 第三章 結果與討論………………………………………….……......49 3.1 矽倍半氧八聚體複合材料之結構鑑定 ……….………….……..49 3.2 光學性質與光物理性質分析 …………………………….……...52 3.2.1 紫外光-可見光光譜分析………………………….….........52 3.2.2 螢光放射光譜分析………………………………….…......61 3.3 能量上轉移的光物理性質探討…………………………….….…63 3.3.1 由螢光放射光譜分析…………………………….……......63 3.4 結論…………………………………………………..…….….…..79 參考文獻 ……………………………………………...………....……81 附錄…………………………………………………………….….…...84

    參考文獻
    1.Iijima, S. Nature 1991, 56, 354.
    2. 實用奈米技術 張安華 主編 新文京開發出版社 民國94 年。
    3. Olsson, K.; Gronwall, C. Arkiv. Kemi. 1963, 17, 529
    4. Brown, J. F. Jr.; Vogt, L. H. Jr.; Prescott, P. I. J. Am. Chem. Soc. 1964,
    86, 1120.
    5. Tamaki, R.; Tanaka, Y.; Asuncion, M. Z.; Choi, J.; Laine, R. M. J. Am.
    Chem. Soc. 2001, 123, 12416.
    6. Laine, R. M.; Choi, J.; Lee, I. Adv. Mater. 2001, 13, 800.
    7. Zhang, C.; Laine, R. M. J. Am. Chem. Soc. 2000, 122, 6979.
    8. Choi, J.; Harcup, J.; Yee, A.-F.; Zhu, Q.; Laine, R. M. J. Am. Chem.
    Soc. 2001, 123, 11420
    9. Tamaki, R.; Choi, J.; Laine, R. M. Chem. Mater. 2003, 15, 793.
    10. Feher, F. J. Organometallics 1991, 10, 2525.
    11. Feher, F. J.; Soulivong, D.; Lewis, G. T. J. Am. Chem. Soc. 1997,
    119,11323.
    12. Feher, F. J.; Terroba, R.; Ziller, J. W. Chem. Commun. 1999, 2153.
    13. Feher, F. J.; Wyndham, K. D. Chem. Commun. 1998, 323.
    14. Harrison, P. G. J. Organomet. Chem. 1997, 542, 141.
    15. Baney, R. H.; Itoh, M.; Sakakibara, A.; Suzuki, T. Chem. Rev. 1995,
    95, 1409.
    16. Bogdan M.; Hieronim M.; Cezary P.; Piotr Pawluc Springer 2009,
    Adam Mickiewicz University, Poland.
    17. Meads J. A.; Kipping F. S.; J. Chem. Soc. 1915, 107,459.
    18. Brown J. F. ; Vogt L. H., J. Am. Chem. Soc. 1965, 87,4313.
    19. Brown J. F., ibid., 1965, 87, 4317.
    20. Laine, R. M.; Choi, J.; Lee, I. Adv. Mater. 2001, 13, 800.
    21. Zhang, C.; Laine, R. M. J. Am. Chem. Soc. 2000, 122, 6979.
    22. BaneyR. H. et al., Chem. Rev., 1995, 95, 1409.
    23. Brown, J. F. Jr.; Vogt, L. H. Jr.; Prescott, P. I. J. Am. Chem. Soc.
    1964, 86, 1120.
    24. Zhang, C.; Laine, R. M. J. Am. Chem. Soc. 2000, 122, 6979.
    25. Choi, J.; Harcup, J.; Yee, A.-F.; Zhu, Q.; Laine, R. M. J. Am. Chem.
    Soc. 2001, 123, 11420
    26. Tamaki, R.; Choi, J.; Laine, R. M. Chem. Mater. 2003, 15, 793.
    27. Feher, F. J. Organometallics 1991, 10, 2525.
    28. Feher, F. J.; Soulivong, D.; Lewis, G. T. J. Am. Chem. Soc. 1997,
    119, 11323.
    29. Feher, F. J.; Terroba, R.; Ziller, J. W. Chem. Commun. 1999, 2153.
    30. Ronald H. B.; Maki I., Akihito S., and Toshio S., Chem. Rev. 1995, 95,
    1409-1430
    31. David B. C.; Paul D. L., and Franck R., Chem. Rev. 2010, 110,
    2081–2173.
    32. Christian B.; Paul T.; Jocelyne M.; Jacques L. and Laure B. C.
    J. Chem. Soc., Dalton Trans., 1997, Pages 1617–1626
    33. Philip G. Harrison, J. Org. Chem., 1997, 542, 141-183.
    34. Kan-Yi Pu; Kai Li, and Bin Liu, Adv. Mater. 2009, 21, 1–4.
    35. Hoon J. C.; D-H H.; J-I L.; Y-K J.; J-H P.; Jonghee L.; S-K L.; H-K
    S., Chem. Mater. 2006, 18, 3780-3787.
    36. Bruce W. M.; John J. M.; Pamela I. C.; Paul-Alain J.; Russell E. M. J.
    Chem. Soc., Dalton Trans., 2001, 1123–1127.
    37. Tanya N. S., Felix N. C., Coordination Chemistry Reviews, 2010.
    38. Radiy R. I.; Denis V. K.; Felix N. C., Chem. Commun., 2005,
    3776–3778.
    39. Islangulov R.R.; Lott J.; Weder,C.;Castellano F. N., J.Am Chem. Soc.
    2007, 129, 12652-12653.
    40. Tanya N. S. ; Felix N. C., J. Phys. Chem. Lett. 2010, 1, 195–200.

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