合成與分析含二芳基乙烯之共軛化合物

Synthesis and Characterization of Conjugated Molecules Comprising Diarylethene

黃佳琪(Chia-Chi Huang)

指導教授 ： 堀江正樹

國立清華大學/工學院/化學工程學系/碩士(2020年)

摘要

二芳基乙烯為近年來廣為研究的分子結構，特殊的光致變色性質為其最大的特色。其中，照光所影響的不只有外觀顏色，共軛與電子結構的改變造成的物理化學變化如分子長度與導電度，亦受眾多研究者關注。不同的官能基帶來不同的光致變化，此有趣的現象擴大了分子應用的範圍，光致共振結構改變也使其被應用在共軛高分子的領域。我們的研究主題為利用麥克默里反應合成含有二芳基乙烯的共軛環狀化合物，並針對其光學性質和單晶結構作特徵分析，再利用此環狀化合物進行開環聚合製造共軛高分子，進行光學特性之分析。此外，我們也致力於合成共軛直鏈狀化合物，以便與高分子作性質比較。
第一章主要介紹光致變色化合物與共軛高分子的基本特性，以及二者主要應用之層面，如光學儲存裝置與有機場效電晶體。此段著重於二芳基乙烯化合物的介紹，講述在眾多光致變色的化合物中，我們選擇二芳基乙烯化合物做為研究對象的契機，以及我們在合成中所使用的反應機制之介紹。
第二章將詳細說明我們的實驗方法與分析結果，觀測反應產物之光致變色與其他性質之改變。實驗內容包含共軛單體與高分子之合成，並進行產物之性質分析與研究，主要著重於可見光吸收光譜、外觀變化與單晶結構。
第三章與第四章講述此實驗之結論與未來的研究方向，而第五章包含詳細的實驗步驟與光譜分析。

關鍵字

光致變色 ； 二芳基乙烯 ； 麥克莫里反應 ； 開環聚合

並列摘要

Diarylethene derivatives have been widely investigated in recent studies, because of their specific photochromic features and the transformation in molecular length and conductivity upon photoirradiation. Such interesting features have also been introduced into conjugated polymers. In this work, we have synthesized multiple conjugated molecules comprising diarylethene. The cyclic molecules are used for the synthesis of the conjugated polymers via ring-opening metathesis polymerization (ROMP). For comparison, linear conjugated molecules have also been synthesized. Analysis of their photochemical/mechanical properties afterward is also a main study in the work.
In Chapter 1, photochromic molecules and reported conjugated molecules are introduced. In addition, their applications such as optical memory storage and organic field-effect transistors (OFETs) are described. Following is the introduction to reaction mechanism used in this work.
In Chapter 2, the synthesis and analysis of cyclic/linear conjugated molecules and polymers comprising diarylethene are described. They were characterized by UV-vis, 1H NMR, HRFD mass spectroscopies and single-crystal X-ray crystallography.
In Chapters 3 and 4, conclusion of our work and future development are described. In Chapter 5, detailed synthesis procedure, 1H NMR, and HRFD-MS spectra of the products are shown.

並列關鍵字

Photochromic ； Diarylethene ； McMurry reaction ； Ring opening metathesis polymerization

參考文獻

1. Irie, M.; Fukaminato, T.; Matsuda, K.; Kobatake, S. Photochromism of diarylethene molecules and crystals: memories, switches, and actuators. Chem. Rev. 2014, 114 (24), 12174-12277.

2. Irie, M.; Seki, T.; Yokoyama, Y., New frontiers in photochromism. Springer: 2013.

3. Finkelmann, H.; Nishikawa, E.; Pereira, G.; Warner, M. A new opto-mechanical effect in solids. Phys. Rev. Lett. 2001, 87 (1), 015501.

4. Horie, M.; Wang, C.-H. Stimuli-Responsive Dynamic Pseudorotaxane Crystals. Mater. Chem. Front. 2019.

5. Morimoto, M.; Irie, M. Photochromism of diarylethene single crystals: crystal structures and photochromic performance. ChemComm. 2005, (31), 3895-3905.