利用三唑並喹喔啉、噻吩、芴及茚並芴 單元建構新穎對稱型染料並探討其雙態 螢光發射及放大自發輻射性質

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姓名

陳彥縈(Yan-Ying Chen) 查詢紙本館藏

畢業系所

化學學系

論文名稱

利用三唑並喹喔啉、噻吩、芴及茚並芴單元建構新穎對稱型染料並探討其雙態螢光發射及放大自發輻射性質
(Development of Novel Symmetric Dyes Based on Triazoloquinoxaline, Thiophene, Fluorene and Indenofluorene units and Investigation of their Dual-State Emission and Amplified Spontaneous Emission Properties)

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摘要(中)

本篇論文成功合成出以三唑並喹喔啉(Triazoloquinoxaline)為核心結構單元的拉電子基並透過更換不同的推電子基來合成出一系列的對稱型螢光分子該系列模型分子簡稱BTAQ系列，再將這些分子進行固態及液態雙態發射(Dual-State Emission；DSE)的線性光學量測以及放大自發輻射(Amplified Spontaneous Emission；ASE)的量測，在這同時我也將本實驗室已畢業碩士班學生徐正昇合成出的螢光染料進行了DSE及ASE的量測，在經過一系列的光學性質量測後我們將數據結果與結構分子進行探討可以得到以下的結論:
(1) Donor-Acceptor-Donor (D-A-D)及 Donor-π-Donor 這兩種對稱型的結構分子在溶液態中皆有良好量子產率的表現。
(2) 在 BTAQ系列中，不同推電子結構單元均會對分子螢光光譜及固態的螢光量子產率產生影響。
(3) 在所有的模型分子中以模型分子(5)及模型分子(7)為最具代表性的螢光分子，兩者在溶液態與固態都有良好的螢光量子產率，在液態中的螢光量子產率皆有99%，固態中亦有70%之水準，可作為高效的螢光材料。
(4) 在 Donor-π-Donor 這個系列中的模型分子皆測量出ASE的行為且
具有較低的ASE閥值，在做為有機固態雷射材料方面是很有潛力的增益介質。
(5) 以 BTAQ作為拉電子結構單元並以茚並芴結構單元做為推電子基
所組合成的模型分子具有相對較低的ASE閥值(Eth) 89.2 μJcm-2，若能解開其背後機制，應對ASE染料的分子設計有極大幫助。

摘要(英)

We have successfully synthesized a series of Donor-Acceptor-Donor (D-A-D) model molecules using triazoloquinoxaline as the central acceptor and various aromatic units as the end groups through multi-step synthetic processes. We have studied the dual-state emission (DSE) and amplified spontaneous emission (ASE) properties these model
compounds (abbreviated as BTAQ series) by corresponding measurement methods. In addition, we put some efforts to study the ASE properties of a linear dye system with generic structure of D-π-D which was synthesized by our former member (Mr. Hsu, Cheng-Sheng). After analyzing the relation between the molecular structures and the obtained optical
properties, the following conclusions can be drawn:
(1) Both D-A-D and D-π-D type molecules exhibit good quantum yield in their solution state.
(2) In the BTAQ series, different electron donor structures will affect the molecular fluorescence spectrum and solid-state fluorescence quantum yields.
(3) Among all the model compound, molecules 5 and 7 exhibit relatively high quantum yields in both solution and solid states.(i.e. 99% in liquid-states and 70% in solid-states) and can be categorized as efficient DSE materials.
(4) The model molecules of D-π-D series have shown efficient ASE behavior with relatively low ASE thresholds, making them promising gain media as organic solid-state laser materials.
(5) The combination of BTAQ unit and indenofluorene moiety may benefit the lowering of the ASE threshold and it would be interesting to realize the underlying mechanism.

關鍵字(中)

★ 雙態螢光發射
★ 放大自發輻射

關鍵字(英)

★ Dual-State Emission
★ Amplified Spontaneous Emission

論文目次

中文摘要 ........................................ i
Abstract........................................ ii
謝誌.............................................iv
圖目錄.......................................... vii
表目錄...........................................ix
第一章.......................................... 1
1-1 雙態發射有機螢光團 .......................... 1
1-1-1 雙態發射起源與介紹 ........................ 1
1-1-2 雙態發射原理與文獻探討 ..................... 3
1-2 放大自發輻射................................. 6
1-2-1 放大自發輻射介紹 .......................... 6
1-2-2放大自發輻射原理及文獻回顧 .................. 6
1-3研究動機及論文架構........................... 9
第二章、分子設計與合成 ......................... 11
2-1模型分子的結構及分子設計 .................... 11
2-2模型分子之合成流程級策略 .................... 14
第三章、線性光學探討 ........................... 21
3-1光學實驗及光學儀器 .......................... 21
3-2溶液態及固態線性光學性質鑑定 ................. 24
3-3溶液態放大自發輻射性質鑑定 ................... 33
3-4 結果與討論 .................................. 44
第四章、實驗儀器及樣品 ........................... 48
4-1 化合物合成之所有藥品與溶劑 ................... 48
4-2 化合物合成之詳細步驟 ......................... 49
第五章、結構鑑定光譜圖 ........................... 76
參考文獻 ....................................... 105

參考文獻

[1] Hoche, J.; Schmitt, H. C.; Humeniuk, A.; Fischer, I.; Mitric, R.; Rohr, M. I. S. The mechanism of excimer formation: an experimental and theoretical study on the pyrene dimer. Phys. Chem. Chem. Phys. 2017, 19, 25002-25015.
[2] Huber, A.; Dubbert, J.; Scherz, T. D.; Voskuhl, J. Design Concepts for Solution and Solid-State Emitters -A Modern Viewpoint on Classical and Non-Classical Approaches. Chemistry 2023, 29, e202202481.
[3] Belmonte-Vázquez, J. L.; Amador-Sánchez, Y. A.; Rodríguez-Cortés, L. A.; Rodríguez-Molina, B. Dual-State Emission (DSE) in Organic Fluorophores: Design and Applications. Chem. Mater. 2021, 33, 7160-7184.
[4] Xu, Y.; Ren, L.; Dang, D.; Zhi, Y.; Wang, X.; Meng, L. A Strategy of "Self-Isolated Enhanced Emission" to Achieve Highly Emissive Dual-State Emission for Organic Luminescent Materials. Chemistry 2018, 24, 10383-10389.
[5] Jian, N.; Qu, K.; Gu, H.; Zou, L.; Liu, X.; Hu, F.; Xu, J.; Yu, Y.; Lu, B. Highly fluorescent triazolopyridine-thiophene D-A-D oligomers for efficient pH sensing both in solution and in the solid state. Phys. Chem. Chem. Phys. 2019, 21, 7174-7182.
[6]Calzado, E. M.; Boj, P. G.; Diaz-Garcia, M. A. Amplified spontaneous emission properties of semiconducting organic materials. Int. J. Mol. Sci. 2010, 11, 2546-2565.
[7]Tang, X.; Lee, Y.-T.; Feng, Z.; Ko, S. Y.; Wu, J. W.; Placide, V.; Ribierre, J.-C.; D’Aléo, A.; Adachi, C. Color-Tunable Low-Threshold Amplified Spontaneous Emission from Yellow to Near-Infrared (NIR) Based on Donor–Spacer–Acceptor–Spacer–Donor Linear Dyes. ACS Mater. Lett. 2020, 2, 1567-1574.
[8] Martin, R., Prieto, P., Carrillo, J. R., Rodrigues, A. M., Cozar, A, de., Boj, P. G., Diaz-Garcia, M. A., and Ramirez, M. G., Design, synthesis and amplified spontaneous emission of 1,2,5-benzothiadiazole derivatives, J. Mater. Chem. C. 2019, 7, 996-10007.
[9] Fang, M.; Huang, J.; Chang, S.-J.; Jiang, Y.; Lai, W.-Y.; Huang, W. Ladder-type oligo(p-phenylene)s with D–π–A architectures: design, synthesis, optical gain properties, and stabilized amplified spontaneous emission. J. Mater. Chem. C. 2017, 5, 5797-5809.
[10]Miyaura, N.; Suzuki, A. Palladium-catalyzed cross-coupling reactions of organoboron compounds. Chem. Rev. 1995, 95, 2457-2483.
[11] Ishiyama, T., Murata, M., Miyaura, N., Palladium(0)-Catalyzed Cross-Coupling Reaction of Alkoxydiboron with Haloarenes: A Direct Procedure for Arylboronic Esters, J. Org. Chem. 1995, 60, 7508-7510.
[12] Wolfe, J. P., Wagaw, S., Buchwald, S. L., An Improved Catalyst System for Aromatic Carbon-Nitrogen Bond Formation: The Possible Involvement of Bis(Phosphine) Palladium Complexes as Key Intermediates, J. Am. Chem. Soc. 1996, 118, 30, 7215–7216.
[13]Yamabe, S.; Zeng, G.; Guan, W.; Sakaki, S. Substrate dependent reaction channels of the Wolff-Kishner reduction reaction: A theoretical study. Beilstein J. Org. Chem. 2014, 10, 259-270.

指導教授

林子超(Tzu-Chau Lin)

審核日期

2024-8-19

推文