以雙?啶萘亞醯胺與多酸配位基製備鋅金屬有機框架化合物 : 合成、結構鑑定、二氧化碳吸附與硝基化合物感測

Zinc－Organic Frameworks Based on N-(Pyridin-4-yl)-4-(pyridin-4-yl)-1,8-naphthalimide and Multicarboxylic Acids : Synthesis, Structures, CO2 Adsorption, and Nitro Compounds Sensing

蘇雋皓(Chun-Hao Su)

指導教授 ： 吳景雲

國立暨南國際大學/科技學院/應用化學學系/碩士(2016年)

摘要

一系列具螢光性的有機金屬框架透過鋅金屬與不同的芳香類二酸有機配體所設計並合成出來。[Zn2(1,4-bdc)2(NI-bipy-44)] (1)，[Zn2(2,6-ndc)2(NI-bipy-44)] (2)，[Zn2(bpdc)2(NI-bipy-44)] (3)，[Zn2(1,4-bdc-NH2)2(NI-bipy-44)] (4)，[Zn2(1,3-bdc-NH2)2(NI-bipy-44)] (5) 和 [Zn3.5(1,3,5-btc)2(DMF)(H2O)1.5] (6) 是利用硝酸鋅與雙?啶橋接配體N-(pyridin-4-yl)-4-(pydrin-4-yl)-1,8naphthalimide (NI-bipy-44) 和二酸類化合物經由溶劑熱法合成。
我們利用不同長度的有機配體或是修飾上胺基來得到一系列具有不同孔洞大小與孔洞環境的多孔性結構。化合物1－4具有類似的結構，它們都是三維的層柱狀結構，整體具有二次互穿的特性；化合物5則是二維的蜂巢狀結構，化合物6具有獨特的三維結構。
這些有機金屬框架可用於偵測硝基化合物，有機金屬框架與硝基化合物透過分子間π–π作用力或是氫鍵彼此靠近，經電子轉移機制將主框架的電子轉移至缺電子的硝基化合物上，造成螢光焠熄，達到偵測的效果。
此外，化合物1、2、4和5都表現出對CO2的吸附能力，我們更進一步地計算它們對CO2的等量吸附熱 (Qst)。
我們也研究了這些有機金屬框架化合物對有機染料的吸附能力，但是實驗結果顯示這些有機金屬框架與有機染料之間沒有明顯的分子間作用力，因此對於有機染料沒有吸附能力。

關鍵字

萘亞醯胺 ； 金屬有機框架(MOF) ； 二氧化碳吸附 ； 硝基化合物

並列摘要

A series of fluorescent metal－organic frameworks (MOFs) based on zinc metal and different aromatic dicarboxylate ligands were designed and synthesized. [Zn2(1,4-bdc)2(NI-bipy-44)] (1), [Zn2(2,6-ndc)2(NI-bipy-44)] (2), [Zn2(bpdc)2(NI-bipy-44)] (3), [Zn2(1,4-bdc-NH2)2(NI-bipy-44)] (4), [Zn2(1,3-bdc-NH2)2(NI-bipy-44)] (5), and [Zn3.5(1,3,5-btc)2(DMF)(H2O)1.5] (6) were constructed from the hydro(solvo)thermal reactions of zinc nitrate, N-(pyridin-4-yl)-4-(pydrin-4-yl)-1,8naphthalimide (NI-bipy-44), a well-designed dipyridyl bridging ligand, and dicarboxylic acids (1,4-benzenedicarboxylic acid, 1,4-H2bdc; 2,6-naphthalene dicarboxylic acid, 2,6-H2ndc; 4,4′-biphenyldicarboxylic acid, H2bpdc; 2-amino-1,4-benzenedicarboxylic acid, 1,4-H2bdc-NH2; 5-amino-1,3-benzenedicarboxylic acid, 1,3-H2bdc-NH2 and 1,3,5-benzenetricarboxylic acid, H3btc).
Elongating ligand length and functionalized with amino group would adjust the resulted open-frameworks in different pore size or pore environment. Compounds 1-4 have similar structures suiting a 3D pillared-layer structure, and overall 2-fold interpenetration, while compound 5 has a 2D double-walled honeycomb structure and compound 6 has a 3D unique structure.

The zinc MOFs can be used for detection of nitro-compounds. Through π–π stacking or hydrogen bonding between the main-framework and nitro compounds, a election transfer process would occur from MOFs to nitro compounds, resulting in fluorescence quenching.
In addition, compounds 1, 2, 4 and 5 has shown gas adsorption abilities for CO2, and the isosteric heat of adsorption (Qst) has also be determined.
We have studied adsorption abilities of zinc MOFs for organic dyes, the results demonstrate that the zinc MOFs did not show obvious intermolecular forces with organic dyes, so they do not have adsorption abilities for organic dyes.

並列關鍵字

naphthalimide ； metal－organic framework (MOF) ； CO2 ； nitro compound

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