設計二苯基蒽衍生物應用於能量上轉移系統及其光物理性質探討

以作者查詢圖書館館藏

、以作者查詢臺灣博碩士

、以作者查詢全國書目

、勘誤回報

、線上人數：7

、訪客IP：13.58.182.39

姓名

江威德(Wei-Te Chiang) 查詢紙本館藏

畢業系所

化學學系

論文名稱

設計二苯基蒽衍生物應用於能量上轉移系統及其光物理性質探討
(The Design and Photophysical Properties of Energy Upconversion Systems using Diphenylanthracence Derivatives)

相關論文

★ 含胺基之二苯乙烯衍生物的分子內光誘導電子轉移之C-N斷鍵反應及激態錯合體之研究	★ 新型含1,2,3-三氮唑之雙光子吸收材料的合成及其光學性質探討
★ 紫質衍生物研究：間位苯卟啉分子的鋅離子感測及大環紫質的構型	★ 合成新型蒽的衍生物應用於能量上轉移之研究
★ Squamocin 之合成研究	★ 發展4,4’-亞甲基對苯胺或聯苯胺為骨架的四氯衍生物作為人類麩胺基硫轉移酶抑制劑的合成及構效關係的探討
★ 含有香豆素的石膽酸類似物作為唾液酸轉移酶抑制劑的合成與初步活性測試	★ 石膽酸C4含氟唾液酸轉移酶抑制劑和苯並惡嗪酮相關的螢光探針之合成及生物研究
★ 合成和優化2-(1-乙基-3,5-二甲基-1H-吡唑-4-基)乙-1-胺衍生物和其抗三陰性乳腺癌細胞的體外活性研究	★ 以蛋白質體學探討在大腸桿菌中甲醇利用代謝途徑
★ Data-independent acquisition mass spectrometry analysis for identification of cerebrospinal fluid biomarker of reversible cerebral vasoconstriction syndrome	★ 從手性N-亞磺醯胺進行非對映選擇性磷酯基化反應建構高度選擇性的α-胺基磷酸酯
★ DNA型式碳水化合物抗原之生物偵測器的開發及應用	★ 合成具有分子腳架之多並苯化合物且用於自組裝分子薄膜之研究
★ 1,3-偶極環化加成反應在藥物合成與醣晶片上的應用	★ 平面化寡聚萘分子之合成及其光學、電學性質研究

檔案

[Endnote RIS 格式]

[Bibtex 格式]

[相關文章]

[文章引用]

[完整記錄]

[館藏目錄]

[檢視]

[下載]

本電子論文使用權限為同意立即開放。
已達開放權限電子全文僅授權使用者為學術研究之目的，進行個人非營利性質之檢索、閱讀、列印。
請遵守中華民國著作權法之相關規定，切勿任意重製、散佈、改作、轉貼、播送，以免觸法。

摘要(中)

近年來科學家們對於利用低能量的光產生高能量的光產生興趣，其中一種方法便是利用發光團吸收低能量的入射光，經由系統間跨越後將能量轉移至另一個發光團，並且由三重態-三重態消滅機制(triplet-triplet annihilation，TTA)而產生上轉移螢光。
本實驗以rose bengal衍生物為敏化劑，分別設計兩個發光體，在四氫呋喃和甲醇混合溶液中組合成此能量上轉移系統。一個是利用長碳鏈連結兩個發光單體的DMEPA (1,4-bis(2,4,6-trimethyl-3-((10-phenylanthracen-9-yl)
ethynyl)phenyl) butane)，增加其分子碰撞的機會，探討是否有分子內三重態消滅的存在，使得此系統於稀濃度下仍有一定的上轉移螢光表現。此外設計了tBEPA (9-(3,3-dimethylbut-1-yn-1-yl)-10-phenyl-anthrancene)發光體，探討分子結構的改變對其光物理性質及上轉移系統中的影響。
本實驗中兩個系統皆以568 nm激發rose bengal，分別在450 nm 及425 nm可看到DMEPA及tBEPA的上轉移螢光，最佳上轉移螢光量子產率分別為0.0021及0.0052。此外將DMEPA系統與之前實驗室所研究的MEPA、BMEPA系統做比較，發現DMEPA的結構設計無法明顯看到分子內TTA的效果，從發光體濃度與螢光強度的關係來推測，DMEPA於低濃度下存在著分子內的自我淬息使得效果不如預期。

摘要(英)

In recent years, scientists are interested in energy upconversion, i.e., the generation of higher energy photons with respect to incident light. Photon upconversion via triplet-triplet annihilation is a possible way.
In our work, we used rose bengal derivative as sensitizer and designed two emitters to investigated this upconversion systems in MeOH/THF solution. The emitter, DMEPA (1,4-bis(2,4,6-trimethyl-3-((10-phenylanthracen-9-yl)-
ethynyl)phenyl) butane), is composed of two monomers linked by a long carbon chain. The structure was originally considered to improve the collision possibility, so that we can observe delay fluorescence in dilute concentration. And tBEPA (9-(3,3-dimethylbut-1-yn-1-yl)-10-phenylanthrancene) was also designed to decrease the reabsorbance by sensitizer and investigate the photophysical properties in upconversion system.
In these two systems, we can see delay fluorescence at 450 nm and 425 nm respectively using 568 nm incident radiation. And each of the upconvesion quantum yield is 0.0021 and 0.0052. Moreover, we couldn’t observe intramolecular triplet-triplet annihilation as expected in DMEPA system. The phenomenon may be ascribed to intramolecular self-quenching in dilute concentration.

關鍵字(中)

★ 三重態-三重態消滅
★ 能量上轉移

關鍵字(英)

★ triplet-triplet annihilation
★ energy upconversion

論文目次

摘要.......................................................i
Abstract..................................................ii
目錄.....................................................iii
第一章緒論................................................1
1-1前言...................................................1
1-2歷史與發展.............................................2
1-3光子上轉移的原理及過程.................................3
1-4光敏劑與發射體的特性...................................5
1-5相關文獻回顧...........................................6
1-5-1發光體螢光量子產率的影響............................7
1-5-2敏化劑生命期的影響..................................8
1-5-3三重態能階的探討....................................9
1-5-4薄膜的應用.........................................10
1-6研究動機..............................................12
第二章結果與討論.........................................14
2-1 分子設計............................................14
2-1-1 敏化劑............................................14
2-1-2 發射體............................................14
2-2 合成策略............................................16
2-2-1 DMEPA合成.........................................16
2-2-1 tBEPA合成.........................................21
2-3 光物理性質探討......................................23
2-3-1 基本光物理性質探討................................23
2-3-1-1敏化劑...........................................23
2-3-1-2發射體...........................................24
2-3-2 上轉移螢光性質探討................................29
2-3-2-1實驗過程與條件..................................29
2-3-2-2 Rose Bengal & DMEPA (System 1).................31
2-3-2-3 Rose Bengal & tBEPA (System 2).................35
2-3-3 分子內和分子間性質探討............................39
第三章結論...............................................44
第四章實驗部分...........................................45
4-1 一般敘述：..........................................45
4-2 實驗用藥品..........................................47
4-2-1 合成用藥品.........................................47
4-2-2 測量用藥品........................................48
4-3 實驗步驟............................................49
4-3-1 9-Phenylanthracene (1)...........................49
4-3-2 9-Bromo-10-phenylanthracene (2)..................50
4-3-3 1,4-dimesitylbutane-1,4-dione (3)................51
4-3-4 1,4-dimestiylbutane (4)..........................52
4-3-5 1,4-bis(3-iodo-2,4,6-trimethylphenyl)butane (5)..53
4-3-6 1,4-bis(2,4,6-trimethyl-3-((trimethylsilyl)ethynyl)butane (6)..............................................54
4-3-7 1,4-bis(3-ethynyl-2,4,6-trimethylphenyl)butane (7)55
4-3-8 1,4-bis(2,4,6-trimethyl-3-((10-phenylanthracen-9-yl)ethynyl)- phenyl)butane (DMEPA，8).....................56
4-3-9 9-(3,3-dimethylbut-1-yn-1-yl)-10-phenylanthrancene (tBEPA，9)................................................57
第五章參考文獻...........................................59
第六章附錄 (Supporting Information)......................62
6-1 光物理附圖...........................................62
6-2 NMR附圖.............................................69
6-3 X-ray Data...........................................83

參考文獻

1. Zipfel, W. R.; Williams, R. M.; Clark, S. W.; Bruchez, M. P.; Wise, F. W.; Webb,W. W.; Larson, D. R. Science 2003, 300, 1434.
2. Wang, F.; Liu, X. Chem. Soc. Rev 2009, 38, 976.
3. Parker, C.A.; Hatchard, C.G. Proc. Chem. Soc., London, 1962, APR, 386.
4. Parker, C.A.; Joyce, T.A. Chem. Commun. 1968, 13, 749.
5. J.B. Birks, Photophysics of Aromatic Molecules, Wiley-Interscience, 1970.
6. Stelmakh, G.F.; Tsvirko, M.P. Opt. Spectrosk. 1980, 49, 511.
7. Tanaka, Y.; Azumi, T. Inorg.Chem.1986, 25, 248.
8. Terenin, A.; Ermolaev, V. Trans. Faraday Soc.1956, 52,1042.
9. Parker, C.A.; Hatchard, C.G. ; Joyce, T.A. Nature 1965, 205, 1282.
10. Fulton, R.L.; Gouterman, M. J. Chem. Phys. 1961, 35, 1059.
11. (a) Islangulov, R.R.; Castellano, F.N. Angew. Chem. Int. Ed. 2006, 45, 5957. (b) Zhao, W.; Castellano, F. N. J. Phys. Chem. A 2006, 110, 11440. (c) Singh-Rachford, T. N.; Islangulov, R. R.; Castellano, F. N. J. Phys. Chem. A 2008, 112, 3906. (d) Singh-Rachford, T. N.; Haefele, A.; Ziessel, R.; Castellano, F. N. J. Am. Chem. Soc. 2008, 130, 16164. (e) Castellano, F. N.; Singh-Rachford, T. N. J. Phys. Chem. A 2009, 113, 5912.
12. (a) Baluschev, S.; Yakutkin, V.; Wegner, G.; Minch, B.; Miteva, T.; Nelles, G.; Yasuda, A. J. Appl. Phys. 2007, 101, 023101. (b) Baluschev, S.; Yakutkin, V.; Miteva, T.; Avlasevich, Y.; Chernov, S.; Aleshchenkov, S.; Nelles, G.; Cheprakov, A.; Yasuda, A.; Mullen, K.; Wegner, G. Angew. Chem. Int. Ed. 2007, 46, 7693. (c) Baluschev, S.; Yakutkin, V.; Wegner, G.; Miteva, T.; Nelles, G.; Yasuda, A.; Chernov, S.; Aleshchenkov, S.; Cheprakov, A. Appl. Phys. Lett. 2007, 90, 181103. (d) Yakutkin, V.; Aleshchenkov, S.; Chernov, S.; Miteva, T.; Nelles, G.; Cheprakov, A.; Baluschev, S. Chemistry 2008, 14, 9846. (e) Baluschev, S.; Yakutkin, V.; Miteva, T.; Wegner, G.; Roberts, T.; Nelles, G.; Yasuda, A.; Chernov, S.; Aleshchenkov, S.; Cheprakov, A. New J. Phys. 2008, 10, 013007. (f) Miteva, T.; Yakutkin, V.; Nelles, G.; Baluschev, S. New J. Phys. 2008, 10, 013002.
13. Kozlov, D. V.; Castellano, F. N. Chem Commun 2004, 2860.
14. Islangulov, R. R.; Kozlov, D. V.; Castellano, F. N. Chem. Commun. 2005, 3776.
15. Ji, S.; Wu, W.; Guo, H.; Zhao, J. Angew. Chem. Int. Ed. 2011, 50, 1626.
16. Schmidt, T. W.; Cheng, Y. Y.; Fuckel, B.; Khoury, T.; Clady, R. G. C. R.; Ekins-Daukes, N. J.; Crossley, M. J. J. Phys. Chem. A 2011, 115, 1047.
17. Keivanidis, P. E.; Baluschev, S.; Miteva, T.; Nelles, G.; Scherf, U.; Yasuda, A.; Wegner, G. Adv Mater 2003, 15, 2095.
18. Baluschev, S.; Keivanidis, P. E.; Wegner, G.; Jacob, J.; Grimsdale, A. C.; Mullen, K.; Miteva, T.; Yasuda, A.; Nelles, G. Appl Phys Lett 2005, 86, 061904.
19. Baluschev, S.; Jacob, J.; Avlasevich, Y. S.; Keivanidis, P. E.; Miteva, T.; Yasuda, A.; Nelles, G.; Grimsdale, A. C.; Mullen, K.; Wegner, G. Chemphyschem 2005, 6, 1250.
20. Laquai, F.; Wegner, G.; Im, C.; Busing, A.; Heun,S. J. Chem. Phys 2005, 123, 074902.
21. Baluschev, S.; Miteva, T.; Yakutkin, V.; Nelles, G.; Yasuda, A.; Wegner, G. Phys. Rev. Lett. 2006, 97, 143903.
22. Islangulov, R. R.; Lott, J.; Weder, C.; Castellano, F. N. J. Am. Chem. Soc. 2007, 129, 12652.
23. Singh-Rachford, T.N.; Castellano, F.N. J. Phys. Chem. A 2008, 112, 3550.
24. Singh-Rachford, T.N.; Castellano, F.N. Inorg. Chem. 2009, 48, 2541.
25. Singh-Rachford, T.N.; Castellano, F.N. J. Phys. Chem. Lett. 2010, 1, 195.
26. Weder, C.; Singh-Rachford, T. N.; Lott, J.; Castellano, F. N. J. Am.Chem. Soc. 2009, 131, 12007.
27. Chen, H. C.; Hung, C. Y.; Wang, K. H.; Chen, H. L.; Fann, W. S.; Chien, F. C.; Chen, P.; Chow, T. J.; Hsu, C. P.; Sun, S. S. Chem. Commun.2009, 4064.
28.林志威，「合成新型蒽的衍生物應用於能量上轉移之研究」，國立中央大學，碩士論文，民國99年
29. Valdesaguilera, O.; Neckers, D. C. Accounts Chem. Res. 1989, 22, 171.
30. Shi. J.; Zhang, X.; Neckers, D. C. J. Org. Chem. 1992, 57, 4418.
31. Neckers, D. C. J. Photoch. Photobio. A 1989, 47, 1.
32. Mosnaim, D.; Nonhebel, D. C.; Russell, J. A. Tetrahedron 1969, 25, 3485.
33. Stewart, F. H. C. Aust. J. Chem. 1960, 13, 478.
34. Moorthy, J. N.; Natarajan P. Cryst. Growth Des., 2008, 8, 3360.
35. Dehmlow, E. V.; Niemann, T.; Kraft, A. Synthetic Commun. 1996, 26, 1467.
36. Moorthy, J. N.; Venkatakrishnan, P.; Natarajan, P.; Huang, D. F.; Chow, T. J. J. Am. Chem. Soc. 2008, 130, 17320.
37. Bernard Valeur. Molecular Fluorescene, WILEY-VCH, 2002.

指導教授

周大新、侯敦仁
(Tahsin J. Chow、Duen-Ren Hou)

審核日期

2011-7-27

推文