Zinc-Organic Frameworks Based on Dipyridyl and Dicarboxylate Ligands : Synthesis, Structures, Dye Adsorption, and Nitro Compounds Sensing

• Main Authors: OU, CHAN-CHENG, 歐展成
• Other Authors: WU, JING-YUN
• Format: Others
• Language: zh-TW
• Published: 2017
• Online Access: http://ndltd.ncl.edu.tw/handle/2rhxz2

碩士 === 國立暨南國際大學 === 應用化學系 === 105 === This work reports several zinc-based fluorescent metal－organic frameworks (MOFs) involving imide-based bispyridyl ligand, N-(pyridin-4-ylmethyl)-4-(pyridin-4-yl)-1,8-naphthalimide (NI-mbpy-44), and aromatic dicarboxylate ligands. Complexes [Zn2(2,6-ndc)2(NI-mbpy-44)] (1), [Zn(1,4-bdc-NH2)(NI-mbpy-44)] (2), and [Zn(1,4-bdc-NH2)(NI-mbpy-44)(H2O)] (2´) were constructed from the hydro(solvo)thermal reactions of zinc nitrate, NI-mbpy-44, and related aromatic dicarboxylic acids including 2,6-naphthalene dicarboxylic acid (2,6-H2ndc) and 2-amino-1,4-benzenedicarboxylic acid (1,4-H2bdc-NH2). Complex 1 has a 3D pillared-layer structure, showing 2-fold interpenetration. Complex 2 has a 2D double-walled honeycomb structure, showing 2-fold interpenetration, while complex 2´ has a 2D double-walled honeycomb structure similar to that of 2 with inclined 2-fold interpenetration of 2-fold interpenetration which is different from that of 2. It is note that elongating ligand length and functionalized with amino group significantly adjusted, the resultant open-frameworks in different pore size and pore environment. The zinc MOFs are used for detection of nitro compounds. The fluorescence of complex 1 would be effectively quenched by 1,4-dinitrobenzene while that of complex 2 would be strongly quenched by 4-nitrophenol and 2,3-dimethyl-2,3-dinitrobutane. The possible quenching mechanism may be attributed to an electron transfer process from the main-framework to the nitro compounds due to host–guest π–π stacking and/or hydrogen bonding interactions. On the other hand, even if both complexes 1 and 2 are highly porous, they do not show significant CO2 adsorption abilities. Cation-exchange studies have shown that the Zn2+ ions in complexes 1 and 2 can be exchanged by Cu2+ and Ni2+ ions. Furthermore, compounds 1 and 2 and Cu-exchanged sample 1-Cu-MeOH have shown different adsorption abilities towards organic dyes. Complex 1 significantly adsorbed methyl blue, methyl green, methylene blue (MB), malachite green chloride (MG), methyl red (MR), and acid orange 7 (AO7), complex 2 showed its adsorption ability towards methyl blue, methyl green, MB, and MG, and sample 1-Cu-MeOH could adsorptively remove methyl orange (MO), methyl blue, methyl green, MB, MG, MR, AO7, and rhodamine B (RhB) from water.