Synthesis and Nonlinear Optical Property Characterizations of Novel Fluorophores with Multi-Quinoxalinyl Units

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蔡銘育(Ming-Yu Tsai) 查詢紙本館藏

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化學學系

論文名稱

(Synthesis and Nonlinear Optical Property Characterizations of Novel Fluorophores with Multi-Quinoxalinyl Units)

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摘要(中)

本論文的研究目的為系統性的設計與合成數個系列含有Quinoxaline基團之模型分子，希望藉由增加分子的π-電子共軛橋樑與增加分子的分歧數，探討分子結構的改變對雙光子吸收特性的影響。我們透過線性光學的測量結果可以得知模型分子之最大吸收波長、最大放射波長、絕對螢光量子產率與單光子螢光生命期；非線性光學使用奈秒雷射進行雙光子激發效率的量測與光學功率限幅實驗，而使用飛秒雷射進行雙光子激發螢光強度與激發光源強度間關係證實觀察到的螢光是經由雙光子吸收所產生的、雙光子激發截面量測主要使用螢光比較法計算得出。經過一系列的光學實驗操作與探討後，可歸納出以下幾點結果：(1)增加分子中心的π-電子共軛橋樑長度，可以促進提升電子內電荷轉移程度，增加雙光子激發截面值。(2)若增加分子結構之分歧數其雙光子激發效能可以大幅提升。(3)Quinoxaline這類型結構對於雙光子吸收的研究在於其具有較長之螢光生命期，因為此現象容易造成激發態再吸收，可將其運用於光學功率限幅材料中。

摘要(英)

The purpose of this study is the systematic design and synthesis of several series containing the Quinoxaline groups model molecules. We want to explore the molecular changes in the structure of two-photon absorption properties of influence by increase in molecular π-electron conjugated bridge and increase the number of molecular branches. After a series of linear and nonlinear optical measurement and discussion can be summarized as the following results. The first is to increase the molecular center of the π-electron conjugation bridge length, can contribute to enhance the degree of charge transfer in the electronics and increase the two-photon excitation cross section value. The second is increasing the number of molecular branches can Promote dramatically of two-photon excitation performance. The third is Quinoxaline this type of structure have much longer fluorescence lifetime, this behavior is likely to cause the excited state re-absorption, it can be applied to optical power limiting marerials.

關鍵字(中)

★ 雙光子吸收
★ 螢光
★ 自吸收
★ 有機染料

關鍵字(英)

★ Nonlinear optical property
★ two-photon absorption
★ Quinoxalinyl-units
★ fluorene
★ Indenofluorene

論文目次

中文摘要...................................I
英文摘要...................................II
謝誌.....................................III
目錄......................................IV
圖表目錄..................................VII
第一章序論.....................................1
1-1雙光子吸收過程的基本原理..........................1
1-2雙光子吸收材料歷史背景與研究發展...................2
1-2-1 雙光子研究起源...............................2
1-2-2 雙光子吸收材料之發展性 .........................3
1-3雙光子吸收材料之分子設計-文獻回顧...................8
1-3-1 P. N. Prasad與其研究團隊提出之設計概念..........8
1-3-2 S. R. Marder & J. W. Perry與其研究團隊提出之設計概念...11
1-3-3 K. D. Belfield與其研究團隊提出之設計概念........11
1-3-4本實驗室於近年所發展之雙光子染料分子...............12
1-4本論文之研究動機與架構............................14
參考文獻..........................................16
第二章分子設計與合成.............................18
2-1本論文模型分子之分子設計..........................18
2-2模型分子之合成概述...............................22
2-2-1前驅物合成...................................22
2-2-2最終產物合成.................................34
參考文獻.........................................36
第三章光學性質探討..............................37
3-1線性光學性質...................................37
3-1-1吸收光譜之量測...............................37
3-1-2螢光發射光譜之量測............................45
3-1-3絕對螢光量子產率之量測.........................49
3-1-4單光子螢光生命期之量測.........................50
3-1-5討論.......................................50
3-2非線性光學性質.................................66
3-2-1雙光子激發螢光光譜之量測.......................66
3-2-2雙光子激發螢光放光量與激發光源強度之關係圖........69
3-2-3奈秒時域的雙光子激發效率光譜之量測...............74
3-2-4飛秒時域的雙光子激發截面光譜量測................78
3-2-5模型分子在奈秒時域之有效光學功率限幅表現..........82
3-2-6討論.......................................86
3-3彙整與討論....................................87
參考文獻.........................................88
第四章實驗部分.................................89
4-1藥品與溶劑....................................89
4-2實驗儀器與量測條件.............................90
4-2-1化學結構鑑定................................90
4-2-2光學性質量測................................90
4-3詳細合成步驟..................................94
3Ph-4Q之合成...................................133
4Ph-4Q之合成...................................134
FLQ之合成......................................135
2Q之合成.......................................136
2Q-Ph之合成....................................137
2Q-FL之合成....................................138
3Q-Truxene之合成...............................139
化合物(9)之合成..................................94
化合物(10)之合成.................................95
化合物(11)之合成.................................95
化合物(12)之合成.................................96
化合物(13)之合成.................................97
化合物(14)之合成.................................98
化合物(15)之合成.................................99
化合物(16)之合成................................100
化合物(17)之合成................................101
化合物(18)之合成................................102
化合物(19)之合成................................102
化合物(20)之合成................................103
化合物(21)之合成................................103
化合物(22)之合成................................104
化合物(23)之合成................................105
化合物(24)之合成................................105
化合物(25)之合成................................106
化合物(26)之合成................................107
化合物(27)之合成................................107
化合物(28)之合成................................108
化合物(29)之合成................................109
化合物(32a)之合成...............................110
化合物(33a)之合成...............................111
化合物(34a)之合成...............................111
化合物(35a)之合成...............................112
化合物(36a)之合成...............................113
化合物(37a)之合成...............................113
化合物(32b)之合成...............................114
化合物(33b)之合成...............................115
化合物(34b)之合成...............................115
化合物(35b)之合成...............................116
化合物(36b)之合成...............................117
化合物(37b)之合成...............................117
化合物(32c)之合成...............................118
化合物(33c)之合成...............................119
化合物(34c)之合成...............................119
化合物(35c)之合成...............................120
化合物(36c)之合成...............................121
化合物(37c)之合成...............................121
化合物(32d)之合成...............................122
化合物(33d)之合成...............................123
化合物(34d)之合成...............................124
化合物(35d)之合成...............................124
化合物(36d)之合成...............................125
化合物(37d)之合成...............................126
化合物(32e)之合成...............................127
化合物(33e)之合成...............................128
化合物(34e)之合成...............................129
化合物(35e)之合成...............................130
化合物(36e)之合成...............................131
化合物(37e)之合成...............................132
第五章附圖(模型分子之氫、碳譜)..................141

參考文獻

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指導教授

林子超(Tzu-Chau Lin)

審核日期

2012-12-10

推文