四向控制分子開關之構築及其功能研究

Abstract

我們在此論文當中成功的合成出一具有TTF之分子夾1a。我們以文獻上已知之glycoluril為基礎之分子夾2為基礎，與2-thioxo-1,3-dithiole在酸催化下進行縮合反應得到分子夾3。利用triethylene glycol monomethyl ether tosylate在鹼性條件之下修飾分子夾3上之酚基，得到分子夾5a，以Hg(OAc)2進行一個硫氧置換反應得到分子夾6a，以此分子夾與1,3-dithiole-2-thione進行一個HWE反應得到分子夾1a。 我們發現具TTF側臂之分子夾與缺乏電子之大環分子之間可形成大環–分子夾之錯合體。運用鉀離子–穴醚、酸–鹼、氧化–還原、冷卻–加熱等外加刺激，可控制此一大環–分子夾錯合體循環於解離與錯合的二種不同狀態。 由於此二種狀態各自呈現不同顏色，此一大環–分子夾錯合體不但可作為一個四向控制之分子開關，還能模擬一個三輸入NOR邏輯閘的表現。

Herein, we synthesized a TTF contained molecular clip 1a. Under acidic condition, the known molecular clip 2 underwent a condensation reaction with 2-thioxo-1,3-dithiole. The resulting product 3 was then modified on the phenolic groups with triethylene glycol monomethyl ether tosylate to get molecular clip 5a. 5a was treated with Hg(OAc)2 to convert thione into ketone (6a). Then the resulting molecular clip 6a was reacted with 1,3-dithiole-2-thione in presence of P(OEt)3 to afford 1a. We found such TTF contained molecular clip that forms a macrocycle – molecular clip complex with a electronic complementary macrocycle. Four different sets of external stimuli – the K+/[2,2,2]cryptand, NH4+/Et3N, (p-PhBr)3NSbCl6/Zn pairs and heating/cooling cycles – allow the movement of this molecular switch to be controlled between its threaded and unthreaded states. The macrocycle – molecular clip complex not only considered as a quadruply controllable molecular switch but also can be operated by three of these stimuli as a three-input molecular NOR-functioning logic gate that may be monitored by UV-Vis spectroscopy.