臺灣博碩士論文加值系統

一般可自由旋轉螢光分子在固態時常受聚集螢光淬滅效應(Aggregation caused quenching)的影響，熒光會大幅度的銳降。四苯基乙烯(Tetraphenylethene)為著名的發光基團，特別是在聚集態時，其熒光與一般可自由旋轉螢光分子不同不降反升，這種聚集使螢光增強 (Aggregation induced emission)的性質，在過去幾年內受到極大關注，因其可應用在多種領域，例如:發光元件、化學感測器和刺激響應元件等，四苯基乙烯作為具有AIE活性的官能基團廣泛地被研究。

Benzothiadiazole (BT)和ethylenedioxythiophene (EDOT)具有良好的電化學以及光學特性，已被廣泛應用在有機光電元件中，其中BT為強拉電子基，EDOT則為強推電子基。本研究將BT和EDOT衍生物作為推拉電子官能基，經由鈀金屬化合物催化鈴木耦合反應與TPE合成出目標分子，並進行光學性質的測定，包含紫外光-可見光吸收光譜及螢光光譜，討論目標分子之聚集態與螢光強度之關聯以及目標分子應用於金屬感測器上之測定。

The conventional fluorescent molecules suffer from aggregation caused quenching (ACQ) which leads to poor emission in the solid state. Tetraphenylethene (TPE) is a well-known luminophore and in particular is highly emission in the aggregated state. Aggregation induced emission (AIE) has attracted much attention in recent years due to its potential uses in the field of electroluminescent elements, chemical sensors and stimuli-responsive elements. TPE has been widely used to construct AIE-active materials owing to its good AIE performance and feasible preparation.

Benzothiadiazole (BT) and ethylenedioxythiophene (EDOT) were widely used as fluorophores for organic electroluminescent elements due to their unique electronic and optical properties. Herein, we have synthesized a series of TPE-based derivatives containing an electron deficient unit, BT, and an electron donating unit, EDOT, by palladium-catalyzed Suzuki cross-coupling reaction. The optical properties of the resulting molecules were determined by UV-vis absorption and photoluminescence spectroscopy. The relationship between ACQ/AIE effects related to the molecular structure and the potential of the designed derivatives in chemosensors are reported in this thesis.

Abstract I
中文摘要 II
List of content III
Chapter 1. Introduction and Aims 1
1.1 Introduction 2
1.2 Conjugated molecules 3
1.3 Band theory of solid 4
1.4 Aggregation-caused quenching 6
1.5 Aggregation-induced emission 8
1.5.1 Introducion to aggregation-caused emission 8
1.5.2 Restriction of intramolecular motion 10
1.6 Introduction to chemosensors 12
1.6.1 Chemosensors 12
1.6.2 The mechanism of analytes detection 13
1.7 Introduction to tetraphenylethene, benzothiadiazole and ethylenedioxythiophene units 15
1.7.1 Tetraphenylethenes 15
1.7.2 Benzothiadiazoles 17
1.7.3 Ethylenedioxythiophenes 19
1.8 Aims of the project 20
1.9 References 21
Chapter 2. Results and Discussion 23
2.1. Synthesis and characterization 24
2.1.1 Synthetic route to BT and EDOT derivatives 24
2.1.2. Synthetic route to TPE derivatives 28
2.1.3. Synthesis of the designed compounds 31
2.2. Optical properties 38
2.2.1 UV-vis and PL spectra 38
2.2.2. Investigation of AIE properties 39
2.2.3. Responsive properties of molecules on metal ions 42
2.3. References 51
Chapter 3. Conclusions 53
Chapter 4 Exerimental Section 55
4.1 General procedures 56
4.2 Synthesis 57
4.2.1 Synthesis of 2-(tributylstannyl)thiazole (1) 57
4.2.2 Synthesis of 4,7-di(thiazol-2-yl)benzo[c][1,2,5]thiadiazole (2) 57
4.2.3 Synthesis of 5,7-di(thiazol-2-yl)-2,3-dihydrothieno[3,4-b][1,4]dioxine (3) 58
4.2.4 Synthesis of 4-(5-bromothiazol-2-yl)-7-(thiazol-2-yl)benzo[c][1,2,5]thiadiazole (4) 58
4.2.5 Synthesis of 5-bromo-2-(7-(thiazol-2-yl)-2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)thiazole (5) 59
4.2.6 Synthesis of 1,2-Bis(4-bromophenyl)-1,2-diphenylethene (6) 60
4.2.7 Synthesis of 2,5-dioctyloxy-1,4-xylene-bis(triphenylphosphonium)dibromide (7) 61
4.2.8 Synthesis of 1-(4-bromophenyl)-1,2,2-triphenylethan-1-ol (8) 62
4.2.9 Synthesis of (2-(4-bromophenyl)ethene-1,1,2-triyl)tribenzene (9) 62
4.2.10 Synthesis of (2-(4-bromophenyl)ethene-1,1,2-triyl)tribenzene (10) 63
4.2.11 Synthesis of 1,2-diphenyl-1,2-bis(4-(2-(7-(thiazol-2-yl)benzo[c]- [1,2,5]thiadiazol-4-yl)thiazol-5-yl)phenyl)ethane (BT-EDOT-BT) 64
4.2.12 Synthesis of 1,2-diphenyl-1,2-bis(4-(2-(7-(thiazol-2-yl) 2,3-dihydrothieno- [3,4-b][1,4]dioxin-5-yl)thiazol-5-yl)phenyl)ethene (EDOT-TPE-EDOT) 65
4.2.13 Synthesis of 4-(thiazol-2-yl)-7-(5-(4-(1,2,2-triphenylvinyl) phenyl)thiazol-2- yl)benzo[c][1,2,5]thiadiazole (TPE-BT) 65
4.2.14 Synthesis of 2-(7-(thiazol-2-yl)-2,3-dihydrothieno[3,4-b][1,4] dioxin-5-yl)-5- (4-(1,2,2-triphenylvinyl)phenyl)thiazole (TPE-EDOT) 66
Appendix 68

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