Multi-photon Absorption and Amplified Spontaneous Emission Properties of Novel Chromophores Derived from Functionalized Benzotriazole and Fluorene Units: Synthesis and Characterization

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謝伊卡(Novia Eka Setyatama) 查詢紙本館藏

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化學學系

論文名稱

(Multi-photon Absorption and Amplified Spontaneous Emission Properties of Novel Chromophores Derived from Functionalized Benzotriazole and Fluorene Units: Synthesis and Characterization)

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摘要(中)

本論文開發出以苯並三唑 (benzotriazole) 與芴 (fluorene) 為結構單元之模型分子，並探討其多光子吸收與增幅自發放射 (amplified spontaneous emission，簡稱ASE) 之光學性質。我們成功透過Suzuki加成反應取得高產率之目標染料分子 (70-94 %)，並透過核磁共振光譜與質譜確認結構。我們對此系列模型分子進行線性光學與非線性光學性質量測，在線性光學實驗方面，我們量測了線性吸收光譜、螢光光譜、螢光量子產率與螢光生命期；而在非線性光學性質方面，我們以可調波長之飛秒脈衝雷射系統作為激發光源以進行多光子吸收之相關實驗。從實驗結果中我們發現在這些模型分子中，2OMe-DFL-Tr2同時擁有最優異的雙光子與三光子吸收表現。我們也發現推與拉電子官能基的強度亦與分子的雙及三光子吸收效率息息相關。另外，此系列之分子結構雖為D-π-A-π-D之對稱模型分子，卻擁有非常明顯的溶劑效應。當我們將模型分子溶於甲苯進行光穩定性實驗時，發現具有甲氧基團 (-OMe) 之模型分子在長時間的UV燈照射下皆較不穩定。另一方面，我們將此系列分子以355 nm的奈秒雷射橫向激發以進行ASE實驗時，發現此系列分子中，2FL-Tr2、2DFL-Tr2及2OMe-DFL-Tr2具有雙重ASE之光學性質，未來將會針對此有趣的光物理現象進行更深一步的研究。

摘要(英)

A new set of model chromophores derived from functionalized benzotriazole and fluorene has been designed and synthesized to investigate of their multi-photon absorption and amplified spontaneous emission (ASE) properties. All model chromophores were synthesized by Suzuki reaction as the final coupling step and were obtained in high yields (70–94%). The structure confirmation of the precursors and model chromophores were determined by 1H NMR, 13C NMR and HRMS. The linear optical properties including absorption spectra, fluorescence spectra, fluorescence quantum yields and lifetime of these model chromophores were investigated by the corresponding spectrometers. As for the multi-photon absorption properties, we have utilized a wavelength-tunable femtosecond laser system to carry out multi-photon-excited fluorescence (MPEF) experiments. The experimental result show that “2OMe-DFL-Tr2” manifests the strongest two-photon and three-photon absorption (2PA and 3PA) among congeners. It is also found that the strength of electron-donors and electron-acceptors are crucial to the molecular 2PA and 3PA. Moreover, all the model chromophores with generic structure of D--A--D possess strong solvatochromic behavior despite of their symmetric nature in the molecular skeleton. We also have tested the photostability of the studied chromophores in solution phase and have found those structures with methoxy groups (i.e. -OMe group) are comparatively unstable under prolonged irradiation of UV-light. On other hand, all the studied model chromophores manifest ASE properties when transversely pumped by a nanosecond laser at 355 nm. It is also found that three of the investigated chromophores (i.e. 2FL-Tr2, 2DFL-Tr2, and 2OMe-DFL-Tr2) exhibit dual-ASE and further studies about such an interesting phenomenon is currently undergoing.

關鍵字(中)

★ 苯並三唑

關鍵字(英)

★ Benzotriazole

論文目次

ABSTRACT ............................................................................................................................... i
ACKNOLEDGEMENT ............................................................................................................ iii
TABLE OF CONTENTS .......................................................................................................... iv
LIST OF FIGURE ..................................................................................................................... vi
LIST OF TABLE ........................................................................................................................ x
LIST OF ABBREVIATIONS AND SYMBOLS ...................................................................... xi
Chapter 1. .................................................................................................................................. 1
Introduction ............................................................................................................................... 1
1.1 Backgound ..................................................................................................................................... 1
1.2 Purpose of this Research ................................................................................................................ 2
1.3 Organization of Thesis ................................................................................................................... 2
1.4 Reference ....................................................................................................................................... 3
Chapter 2. .................................................................................................................................. 4
Organic Compound with multi-photon and/or ASE properties: A brief review ........................ 4
2.1 Organic Compounds with Multi-photon Absorption (MPA) Properties ........................................ 4
2.2 Organic Compounds that exhibit ASE Properties .......................................................................... 6
2.3 Organic Compounds that Multi-photon absorption and ASE Properties ..................................... 10
2.4 Molecular Design of Chromophores in this research ................................................................... 10
2.5 Reference ..................................................................................................................................... 13
CHAPTER 3 ...................................................................................................................................... 15
EXPERIMENTAL SECTION ........................................................................................................... 15
3.1 Synthetic Procedure...................................................................................................................... 15
3.1.1 Synthetic Procedure of Central Core .....................................................................................15
3.1.2 Synthesis Peripheral Compounds ..........................................................................................17
3.1.3 Synthesis Procedure of Target Compounds ..........................................................................21
3.2 Optical Measurement ................................................................................................................... 23
3.2.1 Linear optical measurement ..................................................................................................23
3.2.2 Quantum Yield and Lifetime .................................................................................................23
3.2.3 Solvatochromism ...................................................................................................................23
3.2.4 Photostability Measurement ..................................................................................................24
3.2.5 Two-Photon Excited Fluorescence (2PEF) Measurement ....................................................24
3.2.6 Three-photon Induced Fluorescence (3PEF) Measurement ..................................................25
3.2.6 Amplified Spontaneous Emission (ASE) ..............................................................................26
v
3.3 Reference ..................................................................................................................................... 27
CHAPTER 4 ............................................................................................................................. 29
RESULT AND DISCUSSION ................................................................................................. 29
4.1 Linear Optical Properties .........................................................................................................30
4.1.2 Two photon excited fluorescence (2PEF) .............................................................................37
4.1.3 Three-photon absorption (3PA) Properties ...........................................................................41
4.2 Amplified Spontaneous Emission (ASE) Properties .................................................................... 44
4.3 Photostability ............................................................................................................................... 49
4.4 Conclusion ................................................................................................................................... 52
4.5 Reference ..................................................................................................................................... 53
CHAPTER 5. ............................................................................................................................ 54
DETAILED SYNTHETIC PROCEDURE .............................................................................. 54
CHAPTER VI ........................................................................................................................... 76
SPECTRAL DATA FOR STRUCTURE CHARACTERIZATION ....................................... 76

參考文獻

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指導教授

林子超(Tzu-Chau Lin)

審核日期

2020-8-17

推文