邱勝賢臺灣大學：化學研究所劉彥麟Liu, Yen-LinYen-LinLiu2007-11-262018-07-102007-11-262018-07-102004http://ntur.lib.ntu.edu.tw//handle/246246/51899當雙苄基銨離子(dibenzylammonium ion)以客體形式，穿透尺寸大小適合的冠醚(crown ether)分子中心時，冠醚分子上的氧原子會和銨離子之氮－氫鍵上的氫形成[O…H—N+]形式的氫鍵，進而形成準車輪烷(pseudorotaxane)構形的穩定錯合物。以冠醚－雙苄基銨離子間的氫鍵非共價作用力為基礎，我們嘗試著經由不同的策略來合成一個新型的三維籠狀冠醚分子。我們冀望這樣的籠狀分子與相對應的客體間除了具有多個冠醚與銨離子間的[N+—H…O]氫鍵作用力外，還能利用三維結構中芳香環與芳香環間的π-π疊合作用(π-π stacking)來增強其主客體間的非共價作用力，進而形成一個具有強大鍵結能力的分子辨識系統。It is known that dibenzylammonium ion (DBA+) can complex to dibenzyl[24]crown-8 (DB24C8) and generate the corresponding pseudorotaxane complexes in solution based on the [O…H—N+] hydrogen bonding interaction between both components. We plan to synthesize several three-dimensional cage-liked crown ethers, which can complex to their proper guest not only with the assistance of the multiple hydrogen bonding interactions but also the π-π stacking interaction between the aromatic rings of the cage-liked crown ethers and guests. The binding strength between these crown ethers and their proper guests is expected to be much stronger than that between DB24C8 and DBA+ based on the multivalency concept. The extremely strong binding strength in this new recognition system certainly will allow us to construct many complicated functional interlocked molecules in the future.摘 要………………………………………………………………………I 目 錄………………………………………………………………………III 式 子………………………………………………………………………V 圖 表………………………………………………………………………VI 表 格………………………………………………………………………VIII 壹、緒 論…………………………………………………………………1 1.1 前言……………………………………………………………………1 1.2 冠醚的起源……………………………………………………………2 1.3 主客化學…5 1.4 穴窩體(Cryptand)與球形物(Spherand)……………………………5 1.5 準車輪烷(pseudorotaxane)…………………………………………7 1.5.1 DB24C8和DBA+的系統…………………………………………9 1.5.2 DB24C8和BPE2+的系統………………………………………10 1.5.3 三維立體結構的冠醚分子…………………………………………11 貳、結果與討論…………………………………………………………13 2.1 研究動機……………………………………………………………13 2.2 籠狀冠醚分子1的製備……………………………………………16 2.3 小型三維籠狀分子…………………………………………………28 2.4 其他籠狀冠醚分子的研究…………………………………………32 參、其他研究……………………………………………………………34 3.1 前言…………………………………………………………………34 3.2 研究動機……………………………………………………………36 肆、結論…………………………………………………………………40 伍、實驗部分……………………………………………………………41 陸、參考文獻……………………………………………………………61 附 錄：1H與13C核磁共振光譜…………………………………………662601462 bytesapplication/pdfen-US冠醚籠狀分子crown ethercagethesishttp://ntur.lib.ntu.edu.tw/bitstream/246246/51899/1/ntu-93-R91223068-1.pdf