1.利用酸鹼、溫度及溶劑極性控制之分子開關的合成與性質研究
2.有機-無機超分子錯合物的自組裝合成、結構鑑定與性質探討

本論文包含三部分，第一章在探討所設計出的[2]準車輪烷分子，藉由不同的調控方式來形成分子開關元件的研究。第二章為半剛性含氮有機配子為主體，與銅及鈷金屬鹽錯合形成多樣化的分子構形，並探討構形間轉換機制及化合物的磁性特質。第三章為利用含氮及多羧酸有機配子形成具有孔洞性質的配位聚合物，其具有吸附客分子之能力。第一章中，製備以哌嗪(piperazine)及N,N′-二甲基乙二胺(N,N′-dimethylethylendiamine)為中心核的含氮桿狀分子，經質子化後與冠醚大環分子dibenzo[24]crown-8 (DB24C8)錯合形成[2]準車輪烷分子，並利用酸/鹼調控、溶劑極性及溫度變化來達到控制彼此錯合與解離的分子機械運動行為。第二章中，我們合成出半剛性多芽基有機配子o-H3tpat和m-H3tpat，配子本身具有的柔軟度(Flexibility)及低對稱性(Low-Symmetry)，在與不同金屬離子配位時，可藉由電子共振及幾何異構物間的構形轉換調整出最適合的配位及堆疊模式。有機配子o-H3tpat與CuCl2及Cu(NO3)2配位可分別形成一維鏈狀化合物(1)及(2)，與Cu(ClO4)2於不同溶劑下可形成M8L4的籠形分子結構(3)及(4)；有機配子m-H3tpat與CuCl2及CoCl2則分別形成環形分子構形(5)及一維鏈狀構形(6)。我們另以核磁共振光譜觀測及理論計算證實有機配子o-H3tpat異構物間的構形轉換。此外我們亦探討化合物(1)及(2)的磁性行為表現。第三章中，在有機-無機金屬配位聚合物的合成中，利用末端具有高配位能力的吡嗪及吡啶環官能基並以可撓曲(flexiblity)特性的中心核連接形成含氮有機配子bpzpip、pp-dpma、mm-dpma，並以混合配子方式加入多羧酸有機配子H2BDC、H2NDC、H3BTC及具有手性特性的D-H2Cam分子，預期在與多種金屬鹽配位可形成具有不同特性的配位聚合物。在化合物(7)及(8)中，藉由導入手性的樟腦酸分子可引導出分子內具有等量M-helix及P-helix的一維螺旋結構；化合物(9)和(11)中藉由分子堆疊可形成二維層狀結構，化合物(10)為三維且內部具有一維分子渠道的孔洞結構，在其客分子吸脫附測試中，可藉由熱重分析及紅外線光譜儀觀測對於客分子的吸附量及熱穩定性；化合物(12)、(13)與(14)為利用有機金屬鹽Zn(DBM)2與有機配子mm-dpma於不同溶劑下長晶所得，有相類似的一維分子架構。化合物(13)和(14)均藉由與溶劑分子間產生分子間氫鍵作用力而使其溶劑分子能穿插於分子鏈間，形成一維的溶劑分子渠道，並可藉由吸脫附實驗可置換結構中的客分子種類。

關鍵字

超分子化學； [2]準車輪烷；分子開關；配位聚合物；自主裝合成

並列摘要

This thesis involves three parts: In part 1, a series of pyridine- and pyrazine-containing rod-like molecules was synthesized. In solution, rod-like molecules can be complexed with dibenzo[24]crown-8 (DB24C8) to form [2]pseudorotaxane by intermolecular hydrogen bonding and π-π interactions. We also can control the association and dissocation of the [2]pseudorotaxane complex by adding acid/base, changing temperature, and adjusting solvent polarity of the solvent system. In part 2, two noval tripodal semi-rigid ligands, o-H3tpat and m-H3tpat, consisting of triazine central core and three pyridine donating functions attached to flexible -NHCH2- arms have been designed and synthesized. Self-assembly of o-H3tpat and m-H3tpat with Cu2+ and Co2+ ions form a series of coordination complexes, including 1-D polymer chain structures ((1), (2) and (6)), discrete M8L4 cage structures ((3) and (4)) and metallacyclophane structure (5). Magnetic studies reveal that in (1) every two Cu centers are antiferromagnetically coupled via the chloride bridges. For (2), very weak antiferromagnetic interactions are observed between the Cu centers. In part 3, the goal of this part is to develop a self-assembly strategy for preparation of coordination polymers using flexible N-donor ligands (bpzpip, mm-dpma, pp-dpma) and polycarboxylate O-donor ligands (D-H2Cam, H2BDC, H2NDC, H3BTC). Chiral complexes (7) and (8) are isostructural and both display a (4,6)-connected net in topology hiding a pts-net of square-planar and tetrahedral nodes. Complexes (9) and (11) both adopt a 2-D brickwall structure, which expands into a 3-D supramolecular net through the connection of hydrogen bonds. Complex (10) adopts a 3-D structure, which has a (412•63)-pcu topology. Complexes (12), (13) and (14) all exbibit a 1-D polymer chain structure. The adsorption properties of complexes (9), (10), (11), exhibit that all of them are capable of adsorbing H2O, but only (9) and (10) show the adsorption behavior to pyridine molecules. On the other hand, desolvated complex (13) is capable of adsorbing CH2Cl2 or CHCl3.