跳到主要內容

臺灣博碩士論文加值系統

(3.238.204.167) 您好!臺灣時間:2022/08/13 11:10
字體大小: 字級放大   字級縮小   預設字形  
回查詢結果 :::

詳目顯示

我願授權國圖
: 
twitterline
研究生:李英傑
研究生(外文):Li Ying Chieh
論文名稱:二芐環庚烯酮及吨酮為骨架之螺旋烯在液晶光學開關和電致發光材料的探討與應用
指導教授:陳建添陳建添引用關係
指導教授(外文):Chen Chien-Tien
學位類別:碩士
校院名稱:國立臺灣師範大學
系所名稱:化學研究所
學門:自然科學學門
學類:化學學類
論文種類:學術論文
論文出版年:2002
畢業學年度:90
語文別:中文
中文關鍵詞:液晶光學開關電致發光材料螺旋烯
外文關鍵詞:helicenes
相關次數:
  • 被引用被引用:0
  • 點閱點閱:116
  • 評分評分:
  • 下載下載:0
  • 收藏至我的研究室書目清單書目收藏:1
螺旋烯類化合物的結構由於上、下盤發光團的立體障礙而造成不共平面特性。而此類化合物於基態吸收能量而躍遷至激發態之時,位於連結上下盤的雙鍵部份會形成雙自由基狀態,而此雙自由基激發態欲回到基態釋放能量的方式有兩種:一、 吸收能量後,所形成的雙自由基部分,由於雙鍵特性已消失,能量可由分子轉動形成另一異構物而釋放,形成另一異構物。二、所吸收的能量由於轉動能障較大而趨向由放光方式回到基態。而本論文所採取的兩種系統,第一種為上盤以吨酮及衍生物和二芐環庚烯酮衍生物為基本骨架而下盤採用單一苯環C(2)具L-menthol及(1R,2S)-2-(1-Methyl-1-phenylethyl)-cyclohexanol光學輔助基合成的螺旋烯類化合物。除上盤結構吨酮合成的螺旋烯前驅物:環硫化合物,無法直接以管柱層析法加以分離外,其餘皆可以直接以管柱層析法加以分離,而得到純的兩種異構物。此類環硫化合物在分離後,以六甲基磷醯胺在0℃下進的去硫反應也可分別得到個別非鏡像異構物的螺旋烯,配合HPLC沖堤順序及CD激發子掌性(exciton chirality)的關係來判斷螺旋烯絕對立體化學。而對於此類螺旋烯化合物,我們也進行了其光化學行為及光學開關的探討。
而本實驗室在發展各種不同類型的螺旋烯化合物,研究其光物理行為時發現當改變不同上下盤結構時會有明顯不同系統區分,上述上盤以二芐環庚烯酮為基本骨架者為第一種系統,而本論文另一系統為上盤為二芐環庚烯酮以及下盤為β-naphthoflavine為骨架的螺旋烯類化合物即屬第二種系統,其能量釋放方式較接近於第二種系統,我們利用結構上的差別,能使得第二種系統的吸收光譜到達λmax = 358 nm (in n-Hexane),而其放射波長亦可達到藍光範圍(λmax = 471nm in n-Hexane),我們利用此特性將其應用到有機電致發光二極體元件(OLED)上。雖無令人滿意的結果,但此類分子的設計仍有極大空間,相信對於在OLED此領域新型材料的開發將有所幫助。

The triarylethenes synthesized adopt helical shapes( helicenes) due to the steric overlap of symmetrical upper-part (dibezosuberene derivatives or thioxanthen-9-one and its derivatives) and the unsymmetrical lower part ( .-tetralone at (C2) substituted with chiral auxilary or naphthoflavine). The chirality in these inherently pseudoenatiomeric alkenes, was denoted as M or P for left- or right-handed helical structure. When the steric overcrowded alkenes were excited to the singlet excited states, the double bond connecting both parts would exhibits diradical character. It has been documented that the relaxation of the transition state to the ground state proceeds through two ways: Route I, planarization around the diradical single bond to make the torsional and ring strain to a perpendecular excited state enroute to another photostationary isomer. Route II, the energy relaxation is another phenomena often refer to a general term fluorescenct emission procedure. We have so far examined two systems adopted here, the first system consists of dibenzosuberene derivatives and thioxanthen-9-one and its derivatives upper part and .-tetralone (C2) substituted with L-menthyl and (1R,2S)-2-(1-methyl-1-phenylethyl)-cyclohexyl ester lower part. Except thioxanthen-9-one based episulfides, we can separate the two diastereomers by flash column chromatography. The separated episulfides could be treated under milder desulfurized process by HMPT in ice bath. The absolute configuration of helicenes after desulfuration by HMPT is almost diastereomeric pure, and we also construct the rule in determining the absolute stereochemistry. The last work of this system is the study of photochemistry if the helicenes are suitable for optical switches.
The other system consists of dibenzosuberene upper part and naphthoflavine lower part . The energy relaxation of this system we suggested it to be a fluorescence process ( Route II). We using the difference in energy relaxation route to design the structure based on DBE and naphthoflavine helicenes. The absorption band λmax = 358 nm ( in n-Hexane ) and the emission bandλmax = 471nm ( in n-Hexane ). We applied the compounds to the OLED. The results are not perfect, but we believed it would be helpful for designing new OLED materials.

目錄
中文摘要
英文摘要
第一章 螺旋烯化合物於液晶光學開關的研究與探討
第一節 序論……………………………………………………………………1
第二節 背景 7
第三節 結果與討論 9
一 螺旋烯的合成與實驗步驟 ……………………………………………… . 9
二 絕對立體化學的決定 ….15
三 光化學研究 ….23
第四節 結論 30
第二章 螺旋烯類化合物於有機電致發光二極元件的應用
第一節 序論 32
第二節 β-naphthoflavin類型螺旋烯的合成與實驗步驟 36
第三節 結果與討論 39
一 光物理性質 39
二 螺旋烯25a-c的HOMO、LUMO能階(photolumilenscence; PL) 43
三 元件性質 46
第四節 結論 51
第三章 儀器設備實驗步驟與光譜數據
第一節 分析儀器與藥品 53
第二節 實驗步驟與光譜數據 56
第三節 參考文獻 91
附錄 94

參考文獻
(1) Solladie, G.; Zimmerman, R. G. Angew. Chem., Int. Ed. Engl. 1984, 23, 348.
(2) Feringa, B. L.; Jager, W. F.; de lange, B. Tetrahedron 1993, 49, 8267.
(3) Feringa, B. L.; van Delden, R. A. Angew. Chem., Int. Ed. Engl. 1999, 38, 3418.
(4) (a) Udayakuma, B. S.; Schuster, G. B. J. Org. Chem. 1993, 58, 4165. (b) Huck, N. P.; Jager, W. F.; delange, B.; Feringa, B. L. Science 1996, 273, 1686.
(5) For the photoresolution of molecules with axial chirality, see: (a) Lemieux, R. P.: Schuster, G. B. J. Org. Chem. 1993, 58, 100. (b) Zhang, M.; Schuster, G. B. J. Phys. Chem. 1992, 96, 3063. (c) Zhang, Y.; Schuster, G. B. J. Org. Chem. 1995, 60, 7192. (d) Suarez, M.; Schuster, G. B. J. Am. Chem. Soc. 1995, 117, 6732. (e) Burham, K. S.; Schuster, G. B.; J. Am. Chem. Soc. 1999, 121, 10245. (f) see also: Li, J.; Schuster, G. B.; Cheon, K.-S; Green, M. M.; Selinger, J. V. J. Am. Chem. Soc. 2000, 122, 2603.
(6) eepss stands for the enatiomeric excess of a helicene under a photostationary state at a given irradiation wavelength.
(7) (a) Huck, N. P. M.; Feringa, B. L. J. Chem. Soc., Chem. Commun. 1995, 1095. (b) Feringa, B. L.; Jager, W. F.; de lange, B. J. Chem. Soc. Chem. Comm. 1993, 288. (c) Feringa, B. L.; Jager, W. F.; de lange, B.; Meijer, E. W. J. Am. Chem. Soc. 1991, 113, 5468.
(8) (a) Jager, W. F.; de Jong, J. C.; de lange, B.; Huck, N. P. M.; Meetsma, A.; Feringa, B. L. Angew Chem., Int. Ed. Engl. 1995, 34, 348. (b) Feringa, B. L.; Huck, N. P. M.; van Doren, H. A. J. Am. Chem. Soc. 1995, 117, 927.
(9) For reviews, see: (a) Feringa, B. L.; Huck, N. P. M.; Schoevarrs, A. M. Adv. Mater. 1996, 8, 681. (b) Feringa, B. L.; van Delden, R. A.; Koumura, N.; Geertsma, E. M. Chem. Rev. 2000, 100, 1789.
(10) Koumura, N.; Zijlstra, R. W. J.; van Deden, R. A.; Harada, N.; Feringa, B. L. Nature 1999, 401, 152.
(11) Koumura, N.; Greertsema, E. M.; Meetsma, A.; Feringa, B. L. J. Am. Chem. Soc. 2000, 122, 12005.
(12) Koumura, N.; Greertsema, E. M.; van Gelder, M. B.; Meetsma, A.; Feringa, B. L. J. Am. Chem. Soc. 2002, 124, 5037.
(13) (a) Chen, C.-T.; Chao, S.-D; Yen, K.-C; Chen, C.-H.; Chou, I.-C.; Hon, S.-W. J. Am. Chem. Soc. 1997, 119, 11341. (b) Chen, C.-T.; Chao, S.-D; Yen, K.-C. Synlett 1998, 924. (c) Chen, C.-T.; Chao, S.-D. J. Org. Chem. 1999, 64, 1090.
(14) Chen, C.-T.; Chou, I.-C. J. Am. Chem. Soc. 2000, 122, 7662
(15) 國立台灣師範大學陳建添教授實驗室九十年李泰瑋先生碩士論文。
(16) For a review of asymmetric photochemistry in solution, see: Rau, H. Chem. Rev. 1983, 83, 535.
(17) de Lange, B.; Jager, W. F.; Feringa, B. L. Mol. Cryst. Liq. Cryst. 1992, 217, 127.
(18) Cornelius, L. A. M.; Combs, D. W. Synth. Commun. 1994, 24, 2777.
(19) (a) T. L. 1995, 36, 8715. (b) Lemieux R. P.; Schuster G. B. J. Org. Chem. 1993, 58, 100.
(20) (a) Neureiter, N. P.; Bordwell, F. G. J. Chem. Soc. 1959, 81, 578. (b) Buynak, J. D.; Graff, N. M.; Jadhav, K. P. J. Org. Chem. 1984, 49, 1828.
(21) Harada, N.; Nakanishi, K. Circular Dichroic Spectroscopy-Exciton Coupling in Organic Stereochemistry: University Science Books: Mill Valley, CA, and Oxoford University Press: Oxford, 1983.
(22) 國立台灣師範大學陳建添教授實驗室八十七年高靜儀小姐碩士論文。
(23) 國立台灣師範大學陳建添教授實驗室九十年周怡真小姐博士論文。
(24) Justin Thomas, K.; Lin, J. T.; Tao, Y. -T.; Ko, C. -W. J. Am. Chem. Soc. 2001, 123, 9404
(25) (a) Sander, R.; Stumpflen, V.; Wendorff, J. H; Greiner, A. Macromolecules 1996, 29, 7705.
(b) Adachi, C.; Tsutsui, T.; Saito, S. Appl. Phys. Lett. 1990, 56, 799.
(c) Adachi, C.; Tsutsui, T.; Saito, S. Appl. Phys. Lett. 1989, 55, 1489.
(26) (a) Diez-Barra, E.; Garcia-Martinez, J. C.; Riansares del Rey, S. M.; Rodriguez-Lopez, J.; Sanchez-Verdu, P.; Tejeda, J. J. Org. Chem. 2001, 66, 5664.
(b) Segura, J. L.; Gomez, R.; Martin, N.; Guldi, D.M. Org. Lett. 2001, 3, 2645.
(27) Yang, J. -S.; Chiou, S. —Y.; Liau, K. -L. J. Am. Chem. Soc. 2002, 124, 2518.and references therein.
(28) J. Chem. Soc. Perkin Trans. 1985, 1837.
(29) Feringa B. L. Recl. Trav. Chim. Pays-bas, 1993, 112, 376.
(30) Schoenberg; Stolpp.Chem. Ber. 1930, 63, 3102.
(31) Chauhan, P. M. S.; Rao, K. V. B.; Iyer, R. N.; Shankhadhar, Veena; Gura, P. Y.; Sen, A. B. Indian J.Chem.Sect.B. 1987, 26, 248.(20)
(32) Trahanovsky, W. S.; Tunkel, J. L.; Thoen, J. C.; Wang, Y. J. Org . Chem. 1995, 60, 8407.(21)
(33) Campbell, T. W.; Ginsig, R.; Schmid,H. Helv. Chim .Acta. 1953, 36, 1489.(22)
(34) Yanada, R.; Bessho, K.;Yanada, K. Chem. Lett. 1994, 1279.(23)

QRCODE
 
 
 
 
 
                                                                                                                                                                                                                                                                                                                                                                                                               
第一頁 上一頁 下一頁 最後一頁 top