含雙醯胺雙吡啶與雙羧酸配位基配位高分子的分子感測與表面改質

本論文合成一系列由4,4-oxybis(N-(pyridine-4-yl)-benzamide) (L1), N,N’-bis(3-pyridylmethyl)oxalamide (L2), N,N’-bis(4-pyridylmethyl)oxalamide (L3), 與雙羧酸配位基建構而成的配位高分子，並探究其結構、物理化學性質、氣體吸脫附與光學感測應用性。第I部分：此章節介紹雙醯胺雙吡啶配位基，並探討其與剛性的雙羧酸配位基搭配，所合成的配位高分子。此類配位高分子可應用於揮發性有機物(VOCs)、金屬離子與農藥檢測領域。表面疏水性的應用亦將加以探討。第II部分：將金屬鋅、鎘與鈷之二價鹽類與角型配位基4,4-oxybis(N-(pyridine-4-yl)-benzamide), L1與雙羧酸配位基naphthalene-1,4-dicarboxylic acid (1,4-H2NDC)在數種溶劑下以反應，成功得到3種配位高分子[Zn(L1)(1,4-NDC)·H2O]n, 1, [Cd(L1)(1,4-NDC)(H2O)·MeOH]n, 2, and [Co(L1)(1,4-NDC)(H2O)·MeOH]n, 3。化合物1 - 3 具有8-fold交互貫穿骨架，經過簡化得到拓樸學代號為dia的結構。其孔隙率通過 CO2 吸附得到證實。化合物1和2在水中展現出優異的穩定性，且對於均三甲苯分子和 Fe3+ 離子展現出高選擇性、低偵測極限，及可重複利用等性質。第III部分：將N,N-di(3-methylpyridyl)oxalamide (L2)與N,N-di(4-methylpyridyl)oxalamide (L3)搭配4,4’-hexafluoroisopropylidenebis(benzoic acid) (H2FIPBB)與4,4’-oxybis(benzoic acid)(H2OBA)與金屬鋅、鈷之二價金屬鹽以水熱法反應下可得6種配位高分子，[Zn(L2)0.5(FIPBB)·H2O]n, 4, [Zn(L3)(OBA)·CH3OH]n, 5, [Co(L3)0.5(FIPBB)·CH3OH]n, 6, [Co(L2)0.5(FIPBB)]n, 7, [Co(L2)(OBA)·2H2O]n 8, [Co2(L2)2(FIPBB)2(H2O)5·4H2O]n, 9。化合物6為三維骨架，拓樸學為6T9，化合物7為二維網狀結構，拓樸學為bey。化合物4與5透過CO2的氣體吸脫附證明其孔隙率，並對特定農藥(如: 2,6-dichloro-4-nitroaniline, 2,6-DCN與4-Nitroaniline, 4-NA) 展現出高選擇性、低偵測極限，及可重複利用等性質。此外，通過後合成法(post-synthetic modification, PSM)將長烷基鏈化合物(十八烯)引入化合物4 - 8，改變了各化合物的表面吸水性質，並透過接觸角的量測加以論證。

關鍵字

?? ；晶体?构分析；配位聚合物； ?光特性

並列摘要

This dissertation reports the syntheses, structural characterization, chemical stability, gas absorption analysis as well as detection of sensing properties for small molecules and surface modification of coordination polymers based on the bis-pyridyl-bis-amide (bpba) ligands of 4,4-oxybis(N-(pyridine-4-yl)-benzamide) (L1), N,N’-bis(3-pyridylmethyl)oxalamide (L2), and N,N’-bis(4-pyridylmethyl)oxalamide (L3). In part I, a brief introduction to coordination polymers and functional application as well as characterization methods is presented in this thesis. The synthesis and structures of the bpba ligands are introduced, and the research related to the carboxylate ligands in mixed ligand systems is schematically presented. The coordination polymers in mixed ligand systems can be applied to luminescent sensing of VOCs/metal-ions/pesticides/NACs detection, and to develop hydrophobicity on the surface of CPs through post-synthetic modification (PSM) approaches. In part II, hydro(solvo)thermal reactions of M(II) salts (M = Zn, Cd and Co) with the angular ligand 4,4-oxybis(N-(pyridine-4-yl)-benzamide), L1, and naphthalene-1,4-dicarboxylic acid (1,4-H2NDC) in various solvents afforded [Zn(L1)(1,4-NDC)·H2O]n, 1, [Cd(L1)(1,4-NDC)(H2O)·MeOH]n, 2, and [Co(L1)(1,4-NDC)(H2O)·MeOH]n, 3, which exhibit 8-fold interpenetrating frameworks with the dia topology. Complexes 1 - 2 exhibit porosities substantiated by CO2 adsorption, whereas 1 and 2 manifest stability in aqueous environments, while complex 3 framework show very less durability in chemical media. 1 and 2 have been physical and luminescence characterized, which can influence to sensing exploration. The luminescence studies demonstrated as dual functional sensing behavior for recognition of mesitylene molecules and Fe3+ ions. 1 and 2 strongly intensify its emission in presence of mesitylene molecules with a pronounced selectivity to mesitylene 1.91 and 1.65 for 1 and 2, respectively. Besides, 1 and 2 show high selectivity toward sensing of Fe3+ ions, which represents high quenching efficiency of 95% for 1 and 92% for 2 among other ions in aqueous media, with low detection limits and good reusability up to five cycles. In part III, optimized reactions of N,N-di(3-methylpyridyl)oxalamide (L2) and N,N-di(4-methylpyridyl)oxalamide (L3) with angular dicarboxylic acids of H2FIPBB = 4,4’-hexafluoroisopropylidenebis(benzoic acid), H2OBA = 4,4’-oxybis(benzoic acid), and Zn(II) and Co(II) metal salts afforded [Zn(L2)0.5(FIPBB)·H2O]n, 4, [Zn(L3)(OBA)·CH3OH]n, 5, [Co(L3)0.5(FIPBB)·0.25CH3OH]n, 6, [Co(L2) 0.5(FIPBB)]n, 7, [Co(L2)(OBA)·2H2O]n 8, and [Co2(L2)2(FIPBB)2(H2O)5·4H2O]n, 9. Complex 6 and 7 have been structurally characterized by using single-crystal X-ray diffraction. complex 6 possesses a 3D framework with a 6T9 topology and 7 is a 2D net with the bey topology. Complexes 4 and 5 exhibit porosities vindicated by CO2 adsorption. The activated 4 and 5 exhibited high selectivity toward detection of pesticides such as 2,6-dichloro-4-nitroaniline (2,6-DCNA) and 4-nitroaniline (4-NA) via ‘turn off’ quenching efficiency of 91 and 97 % for 4 and 94 and 98 % for 5, respectively. Furthermore, static titration experimented demonstrated with low detection limits and good recyclability up to five cycles. The post-synthetic modification (PSM) process to integrate long alkyl chains of 1-octadecene into 4 – 8 modified surface wettability induces hydrophobicity, which was demonstrated by water contact angle measurement (WCA).

並列關鍵字

entanglement ； crystal structure analysis ； coordination polymers ； luminescence properties

參考文獻

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