1,2及1,4位雙(吡啶-4-基乙炔基)苯的合成和氧化還原研究

Synthesis and Redox Investigations of 1,2- and 1,4-bis(pyridine-4-ylethynyl)benzenes

徐佩璿(Pei-Hsuan Hsu)

指導教授 ： 徐秀福

淡江大學/理學院/化學學系碩士班/碩士(2021年)

https://doi.org/10.6846/TKU.2021.00796

摘要

近年來中性有機電子供體被廣泛運用在電化學反應、電致變色材料、半導體材料及超分子系統中。因不需透過金屬且具有可逆的電子還原成自由基陽離子和中性形式，對於材料開發可更多元更不受限制。在基態下，它們可對一系列官能團進行無金屬還原。四硫富瓦烯(tetrathiafulvalene, TTF)、四(二甲基胺)乙烯((etrakis(dimethylamino)ethene, TDAE)、四氨基乙烯(tetraazafulvalene, TFA)、雙吡啶亞基(bispyridinylidene, BPL)及紫精(viologens)為常見的系統。
本論文以參考紫精衍生物分子結構擴展紫精(extended viologen)及六(4-(N-烷基吡啶鎓))苯((4-(N-butylpyridylium))benzene)，於單鍵中加入三鍵，延伸出1,2及1,4位雙(吡啶-4-基乙炔基)苯結構分子。預期還原三鍵後可增加共軛，且兩者具有不同的醌形(quinone)結構可藉由此進行比較。實驗將吡啶結合苯乙炔基，再將吡啶上的氮烷化離子化，接著利用鈉汞齊將三鍵還原為雙鍵，增強其共軛並期望能合成出具有強氧化還原的有機電子供體。
本論文成功合成出1,2及1,4位雙(吡啶-4-基乙炔基)苯結構分子，並透過核磁共振光譜儀及質譜儀鑑定確認。雖分子未成功烷化，但確定有離子化。將離子化的分子進行紫外可見光吸收光譜及螢光光譜量測並進行比對，可看出訊號位移且變多，與模擬出的最高占據具分子軌域(HOMO)及最低未占據具分子軌域(LUMO)能階有一致的趨勢。推測分子應具有良好的氧化還原能力、電子具有好的流動性，可能為一個好的電子供體。

關鍵字

有機電子供體 ； 氧化還原 ； 紫精 ； 吡啶 ； 醌體

並列摘要

In recent years, neutral organic electron donors have been widely used in electrochemical reactions, electrochromic materials, semiconductor materials and supramolecular systems. Because these materials don’t need metal and haves reversible electron reduction to free radical cations and neutral forms, it can be more versatile and unlimited for material development. In the ground state, they can perform metal-free reduction of a series of functional groups. Tetrathiafulvalene (TTF), tetrathiafulvalene (TTF), tetrakis(dimethylamino)ethene (TDAE), tetraazafulvalene (TFA), bispyridinylidene (BPL), and viologens are common systems.
By inserting a ethynyl unit between aryls in viologen and hexa(4-(N-alkylpyridinium))benzene, new materials of 1,2- and 1,4-bis(pyridine-4-ylethynyl)benzenes were designed and synthesized. It was expected that after N-alkylation followed by the reduction, quinonoid structures of the two can be formed and the subsequent chemical properties can be compared. Unfortunately, the N-alkylation and subsequent reduction were not successfully achieved as evidenced by NMR, UV-vis, and fluorescence spectroscopic studies.

並列關鍵字

Organic electron donor ； redox ； viologen ； pyridine ； quinone

參考文獻

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