咔唑衍生物由於其富電子的特性,化學穩定性高以及含有延伸之共軛結構特性,在有機光電元件的應用領域上，受到研究並已行之有年。咔唑同時也已其擁有的光學特性以及可調整之電化學特性為特色。
在本研究中，我們藉由鈴木反應、烏耳曼反應及麥克默里反應合成了一環型共軛結構，此結構由二噻吩基乙烯連接咔唑之3號位及9號位所形成。我們亦透過X光單晶繞射儀來定性此分子結構，藉由儀器也看出了此分子排列時的結構：接在咔唑三號位的噻吩基和咔唑形成共平面，接在咔唑九號位的噻吩基則垂直此平面。除此之外，在單晶狀態下也觀測分子呈現波型排列，分子之間亦擁有π-π 電子作用力(π-π interaction)和S···S電子作用力(S···S interaction)。同時也透過1H-NMR光譜和場解析質譜來為分子進行定性分析。在光學特性方面，此分子也因環張力產生了176奈米的斯托克斯位移(Stokes shift)。為了增進聚合後的溶解性，我們用開環聚合(ROMP)的方式，將我們的單體和聚降冰片烯組成了嵌段共聚物。此外，另一個由二噻吩醛基連接咔唑之3號位及9號位組成的分子，雖作為環型共軛分子的前驅物，也展現了其溶液致螢光色變的特性。

Carbazole derivatives have been applied in the field of organic optoelectronics due to their unique properties such as electron-donor, planar structure, extended π-system, facile synthesis and modification, tunable optical and electrochemical properties, and high chemical stability.
In this work, a 3,9-linked dithienyl-carbazole cyclic conjugated molecules have been synthesized by Suzuki coupling, Ullmann condensation, and McMurry coupling. The molecules are characterized by single-crystal X-ray crystallography showing specific structures; planar form between 3-carbazole and 2-thiophene groups but perpendicular form between 9-carbazole and 2’-thiophene groups. In addition, the packing structure showed wavelike arrangement, and intermolecular π-π interaction, intermolecular S···S interaction were observed in the single crystal state. These molecules are also characterized by 1H-NMR and field desorption mass spectroscopy. The optical property of the molecule performed Stokes shifting up to 176 nm due to the ring strain. In addition, a sequence of block polymers of poly(norbonene-block-dithenylcarbazole) are synthesized via ROMP to improve the solubility of the polymers. Moreover, I find that the precursor of cyclic dimer, which is a carbazole with 3,9-substituded thiophenecarboxaldehye, showed fluorescent solvatochromism.

Table of contents
Abstract ----------I
Chapter1 Introduction ----------1
1-1 Introduction to carbazole ----------1
1-1-1 Basic property of carbazole ----------1
1-1-2 Advanced applications of carbazole unit fluorescent properties ----------2
1-2 Conjugated polymers ----------8
1-2-1 Introduction to conjugated polymers ----------8
1-2-2 optoelectronic applications of carbazole-containing polymers. ----------9
1-3 Introduction to synthesis methods ----------16
1-3-1 Suzuki-Miyaura coupling reaction ----------16
1-3-2 Ullmann coupling reaction ----------18
1-3-3 McMurry reaction ----------20
1-3-4 Ring-Opening Metathesis Polymerization (ROMP) ----------21
1-4 Aim of work ----------26
Chapter 2 Synthesis, characterization, and spectroscopic properties of cyclic conjugated molecules and polymers ----------28
2-1 Synthesis and characterization of dithienyl carbazole-containing molecules. ----------28
2-1-1 Synthesis of 3,9-bis(2-thiophenyl) carbazole molecules ----------28
2-1-2 X-ray crystallography of 3,9-bis(2-thiophenyl) carbazole molecules ----------33
2-2 Synthesis and characterization of dithienyl carbazole-containing polymer ----------45
2-3 Spectroscopic properties of dithienyl carbazole-containing molecules in solution. ----------49
2-3-1 UV-vis spectra of dithienyl carbazole-containing molecules and polymer. ----------49
2-3-2 Photoluminescence spectra and photoluminescence quantum yield (PLQY) of dithienyl carbazole-containing molecules and polymer. ----------51
2-4 Spectroscopic properties of dithienyl carbazole-containing molecules and polymers in solid state. ----------54
2-5 Cyclic Voltammetry and energy diagrams of dithienyl carbazole-containing molecules and polymers ----------58
2-7 Fluorescence solvatochromism of dithienyl carbazole-containing molecules ----------61
Chapter 3 Conclusion ----------64
Chapter 4 Future Perspective ----------65
Chapter 5 Experiment section ----------66
5-1 General methods ----------66
5-2 Synthesis of 3,9-bis(2-thiophenyl) carbazole molecules 2-1 and 2-2 ----------67
5-2-1 Synthesis of 5-(9H-carbazol-3-yl)- 2-Thiophenecarboxaldehyde (M1) ----------67
5-2-2 Synthesis of 5-(3,9-9H-carbazole)-2-dithiophenecarboxaldehyde (M2) ----------68
5-2-3 Synthesis of 3,9-bis (2-thiopheyl)carbazole molecules ----------69
5-2-4 Synthesis of carbazole-containing polymer P1 (ROMP) ----------70
5-3 NMR spectra and CV curves of ferrocene ----------71
5-4 Additional Work (Ring opening reaction of 2-1) ----------73
References ----------75

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