臺灣博碩士論文加值系統

具 U-型骨架、多官能基化的二醇 70 之合成，係以狄爾斯亞德環加成物 67 做為合成起始物，經五個步驟的化學轉換合成出二醇 70 。此一 U-型二醇 70 經威廉森醚化反應的方式，與苄基溴、 4-溴苄基溴、 4-碘苄基溴、 9-溴甲基蒽、1-溴甲基芘、溴甲基吡啶反應，可建構一系列蟹狀分子。化合物 70 也可經由鹼促化之酯化反應，與醋酸酐、苯甲醯氯、苯甲酸、 9-酮基茀-2-羧酸反應，製備另一系列具有蟹狀結構之分子夾。其中化合物 105 、 106 、 117 與 118 分子內的發光團側臂會經自組程序形成 p-堆疊，經由單晶結構或發光性質得知其是由於分子內 p-p 作用力所造成，且兩發光團間距離約為 3.4 Å 。另一方面，具雙間位取代吡啶環的蟹狀分子 110 與一價銀離子錯合，可形成 (1+1) 金屬橋接環芃 113 ；而具雙鄰位取代吡啶環的蟹狀分子 111 與一價銀離子錯合，則形成 (2+2) 的雙金屬橋接環芃 114 。 U-型二醇 70 以威廉森醚化反應的方式，與 a,a’-二溴對二甲苯、a,a’-二溴間二甲苯反應，可得到具剛性骨架的 (1+1) 環芃、 (2+2) 環芃與寡聚物。在這些例子中，(2+2) 環芃為主要產物。當二醇 70 與 a,a’-二溴鄰二甲苯反應則是得到 (2+2) 環芃與寡聚物，而並未得到 (1+1) 環芃。

The synthetic route to the U-shaped, multi-functionalized diol 70 begins from the Diels-Alder adduct 67. Through five steps lead to diol 70. The U-shaped diol 70 reacted with benzyl bromide, 4-bromobenzyl bromide, 4-iodobenzyl bromide, 9-(bromomethyl)anthracene, 1-(bromomethyl)pyrene, isomeric bromomethylpridines via Williamson ether synthesis to construct a series of molecular crabs. It also reacted with acetic anhydride, benzoyl chloride, benzoic acid, 9-fluorenone- 2-carboxylic acid via base-promoted esterification to afforded another series molecular tweezers with crab-shaped structure. The self-assembled intramolecular p-stacking of chromophore in 105, 106, 117 and 118 with the distance about 3.4 Å, and the consequent p-p interactions were revealed by the X-ray crystal structure or its luminescence property. On the other hand, the bis-meta-pyridyl crab 110 complexation with silver(I) afforded a (1+1) metallo-bridged cyclophane 113. And the silver(I)-complex 114 from bis-ortho-pyridyl crab 111 is a (2+2) dimeric dimetallocyclophane. The U-shaped diol 70 reacted with a,a’-dibromo-p-xylene and a,a’-dibromo- m-xylene via Williamson ether synthesis afforded (1+1) cyclophanes, (2+2) cyclophanes and oligomers. In these cases, (2+2) cyclophanes were major products. Diol 70 reacted with a,a’-dibromo-o-xylene afforded both (2+2) cyclophane and oligomers. There has none (1+1) cyclophane being isolated.

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