在本論文中，我們報導一系列具三度空間之非平面的triptycene和pentiptycene衍生物的合成，探討分子如何利用氫鍵和π-π相互作用堆疊出固態之超分子結構。首先，我們設計並合成出在triptycene和pentiptycene上有雙取代乙醯胺磺酸酯基的化合物A2和B2，然後測得此兩化合物的x-ray單晶結構。在triptycene衍生物的部份，化合物B2在固態下的分子結構是有趣的彎折構形。經由與化合物B1、B14與B5在固態下不彎折而化合物B4、B8、B13與B16在固態下為彎折的結構比較得知：醯胺基分子內氫鍵、分子內芳香環間之π-π相互作用與磺醯酯基等三部份皆是構成彎折構形的重要關鍵。而在pentiptycene衍生物方面，化合物A2在晶體中的醯胺基間沒有氫鍵產生且形成格子狀隧道結構。為了對pentiptycene這類衍生物在固態中的結構有更深入的了解；我們合成出pentiptycene的衍生物A0、A3、A4、A5、A6和A7。結果顯示pentiptycene間的堆疊方式會因取代基不同而有重大不同，分析歸類後對於日後設計iptycene為主的超分子結構將有很大的助益。 In this thesis, we take advantage of iptycenes as the backbone to design organic supermolecules. We then use the intermolecular interaction such as hydrogen bonds and π-πinteractions to treat the triptycene and pentiptycene derivatives self-assembled. First, we synthesis the triptycene and pentiptycene substituted A2 and B2 with N-acetylsulfanily group. Then they were characterized by single crystal X-ray diffraction. The molecular structure of B2 is folded, and shows an anomalous hydrogen-bonding chain motif. In order to find out the driving force behind the folding of the molecular. We divided the possible driving forces into three parts that is the intramolecular hydrogen bond of amide groups、the intramolecular π-πinteraction of aromatic rings and the sulfanily group. We synthesis a series of triptycene derivatives. The crystal structure of B1、B14 and B5 were unfolded, and B4、B8、B13 and B16 were folded. As evident from the crystals presented, we know the three parts are very important. On the othe hand, the pentiptycene diamide A2 adopts an extended comformation, and the amide groups do not participate in any known amide-amide hydrogen-bonding patterns. Instead, interdigitated molecular stacking results in grid-like channels. Latter, we synthesis various pentiptycene derivatives A0、A3、A4、A5、A6 and A7. The pentiptycene group of them would form several kinds of one-dimensional pillars and then we discuss the stacking of them in two- and three-dimensions. So we could use these results in the design of new organic crystalline architectures.
