哌嗪含錸金屬錯合物：自組裝、結構與性質研究

本論文發展微波快速合成法，製備氨基吡啶和芳香胺的衍生物，並且以此方法和技術為基礎，設計兩個不對稱的分子2-(4-(pyridin-4-yl)piperazin-1-yl)pyrazine(3N-PyPiPz)和2-(4-(pyrimidin-5-yl)piperazin-1-yl)pyrazine (4N-PmPiPz)，並且將它們應用至環形超分子的研究上。環形超分子系列之研究，利用三個含哌嗪 (piperazine) 的有機配子4,4''''-dipyridylpiperazine (2N-DPyP) 、N,N''''dipyrazylpiperazine (4N-DPzP) 、2-(4-(pyridin-4-yl)piperazin-1-yl)pyrazine (3N-PyPiPz)和Re2(CO)10水熱反應得到三角形的環形超分子[Re2(CO)6(2N-DPyP)(DHBQ)] (1) ，和四邊形的環形超分子[Re4(CO)12(4N-DPzP)2(BiBzIm)2] (2)、[Re4(CO)12(4N-DPzP)2(OCH3)4] (3)、[Re4(CO)12(3N-PyPiPa)2 (OCH3)4] (4)。本研究中詳細探討實驗合成方法、結構解析、哌嗪 (piperazine)構形變化的因素、並量測其性質，本實驗盡量使用符合綠色化學規範的方法。

關鍵字

微波合成；自組裝；環形超分子；哌嗪

並列摘要

The goal of this thesis was to improve synthesis of aminopyridines and arylamines using microwave irradiation. Two asymmetric organic ligands, i.e. 2-(4-(pyridin-4-yl)piperazin-1-yl)pyrazine (3N-PyPiPz) and 2-(4-(pyrimidin-5-yl)piperazin-1-yl)pyrazine (4N-PmPiPz),were synthesized using microwave irradiation. Two reaction of Re2(CO)10, 4,4'-dipyridylpiperazine (2N-DPyP), and 2,5-dihydroxy-1,4-benzaquinone (DHBQ) in the presence of toluene under hydrothermal conditions gave [Re2(CO)6(2N-DPyP)(DHBQ)] (1). Reaction of Re2(CO)10,N-N'dipyrazylpiperazine (4NDPzP),and 2-2'-dibenzimidazole (DBZID) under similar reaction conditions produced complex [Re4(CO)12(4N-DPzP)2(DBZID)4] (2). The reaction of Re2(CO)10 with 4N-DPzP or 2-(4-(pyridin-4-yl)piperazin-1-yl)pyrazine (3N-PyPiPz) in the presence of methanol under hydrothermal conditions gave [Re4(CO)12(4N-DPzP)2(OCH3)4] (3) and [Re4(CO)12(3N-Py-PiPa)2(OCH3)4] (4), respectively. By varying the conformation of piperazine, three types of metallacyclic compounds were obtained via self-assembly strategy.