含氮化合物的孔洞材料：設計、合成與物性探討

本論文主要利用偶和片段連接方式合成大環系統，以2Boc-4NH-2Cl為主體，並在環上修飾一系列具立體障礙之官能基團來合成大環單體分子及高分子鏈化合物，其中包含兩大系列，以含有t-butylcarboxylate (Boc)與羧酸基(COOH)兩種系列產物，並分別以三個部分來探討結構與二氧化碳客分子間吸脫附的相互關係。第一部分，以2Boc-4NH-2Cl為主體，兩端側枝分別以morpholine、piperazine與p-phenylenediamine (另一端修飾acetyl chloride)來觀測其構型及陰電性不同所造成對二氧化碳吸脫附及比表面積間的差異，另也藉由加熱方式來將t-butylcarboxylate (Boc)形成羧酸基(COOH)後探討其變化及影響。第二部分，以piperazine和2,7-diazaspiro[4.4]nonane作為連接基將大環分子串聯形成高分子鏈，藉此來觀測及比較與單體分子間的差異性。第三部分，側枝以較長及較大立障的N-tBu-pip基團分別連接2Boc-4NH-2Cl與m-4NH-2Cl兩種大環，探討立障官能基位於側枝或大環上有無t-butylcarboxylate (Boc)官能基對於孔洞性及二氧化碳吸附脫能力的比較與影響。此一系列大環衍生物皆藉由核磁共振光譜及質譜來鑑定及判別化合物的純度，並利用熱重分析儀觀測樣品之熱穩定性及官能基t-butylcarboxylate (Boc)轉換成羧酸基(COOH)之溫度變化值。

關鍵字

大環分子；氫鍵作用力；自組裝；熱穩定性；氣體吸附

並列摘要

This thesis reports the synthesis of macrocyclic system which is adjusted by fragment coupling and it is based on 2Boc-4NH-2Cl to synthesize a macrocyclic molecular and polymer chains’ compound via modifying a series of functional group which have steric effect. It distributed two set on t-butylcarboxylate (Boc) and carboxylic acid (COOH) and included three parts of correlations between investigated structure and carbon dioxide adsorption-desorption. 　　The first part is using morpholine、piperazine and p-phenylenediamine (the other end is modifying acetyl chloride) at both ends on the 2Boc-4NH-2Cl core. It were observing the differences between carbon dioxide adsorption-desorption and BET surface for their structure and electronegative. Besides, the t-butyl group on this macrocyclic molecular products were becoming a carboxylic acid macrocyclic molecular by heating synthesis pathway. The second part is the polymer chains on macrocyclic molecular which with the linker such as piperazine and 2,7-diazaspiro[4.4]nonane. It would compare the different with monomer molecular for carbon dioxide adsorption-desorption. The last part is taking N-tBu-pip which have longer and have bigger steric effect to link on 2Boc-4NH-2Cl core or m-4NH-2Cl core. The steric effect functional group where two ends on the core and the core with t-butylcarboxylate (Boc) functional group or without in order to discuss on porous properties and carbon dioxide adsorption-desorption. 　　Thus a series of macrocyclic derivatives were identified by Nuclear Magnetic Resonance spectroscopy and Mass Spectrometer. Moreover, we studied on their thermal stability and the temperature for t-butylcarboxylate (Boc) being change to carboxylic acid (COOH) by Thermogravimetry Analysis.