以咔唑雙吡啶與對苯二甲酸製備鋅金屬有機框架化合物：合成、結構鑑定與感測行為

Zinc–Organic Frameworks Constructed from Carbazole-Derived Bispyridyl and Substituted 1,4-Benzenedicarboxylic Acids: Synthesis, Structures, and Sensing Behaviors

陳威廷(Wei-Ting Chen)

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(2021年)

https://doi.org/10.6837/ncnu202100087

摘要

本研究透過鈴木偶聯反應(Suzuki-coupling)合成出兩個咔唑雙吡啶有機配體，分別為3,6-bis(pyridin-4-yl)-9H-carbazole (bphc)與9-n-propyl-3,6-bis(pyridin-4-yl) -9H-carbazole (bppc)。以之與硝酸鋅及對苯二甲酸(1,4-H2bdc)和2,5-二羥基對苯二甲酸((OH)2-1,4-H2bdc)經溶劑熱合成法製備出四個金屬有機框架化合物，分別為[Zn(1,4-bdc)(bppc)]‧DMF (1)、[Zn(1,4-bdc)(bphc)]‧DMF (2)、[Zn(1,4-bdc)(bphc)]‧2H2O (3)、[Zn((OH)2-1,4-bdc)(bphc)] (4)。化合物 1、2、4皆為具有二重互穿的二維結構，化合物3是具有四重互穿的三維結構。
陽離子感測實驗中，化合物1與化合物3之水懸浮液對Fe3+離子均有極佳的專一性以及淬熄率，另外化合物3之DMF懸浮液具有高螢光性，用於感測Cu2+、Al3+、Cr3+、Fe3+離子有不同程度的螢光淬熄表現，對三價金屬離子之滴定感測實驗中表現出了兩階段的感測行為。化合物4只具有微弱的螢光，但透過螢光增強效果能選擇性檢測溶液中的Al3+離子。干擾實驗以及偵測極限量測證實化合物1、3、4有良好的選擇性離子感測表現以及低偵測濃度，顯示化合物1、3、4可做為良好的離子螢光感測材料。
酚類以及胺類等有機小分子感測實驗中，化合物1之水懸浮液對酚類和胺類化合物感測並無明顯的淬熄效果。值得注意的是化合物3之DMF懸浮液對於對苯

二胺有良好的感測專一性，能夠從鄰位、間位、對位的苯二胺中選擇性的檢測出對苯二胺，且具有良好的靈敏度及偵測極限，顯示化合物3可做為良好的對苯二
胺感測材料。

關鍵字

金屬有機框架 ； 有機小分子感測 ； 陽離子感測

並列摘要

In this thesis, two organic ligands 3,6-bis(pyridin-4-yl)-9H-carbazole (bphc) and 9-n-propyl-3,6-bis(pyridin-4-yl)-9H-carbazole (bppc) have been synthesized by Suzuki-coupling. Hydrothermal reactions of bphc or bppc with Zn(NO3)2‧6H2O and substituted 1,4-benzenedicarboxylic acids yielded four new metal–organic frameworks (MOFs), namely [Zn(1,4-bdc)(bppc)]‧DMF (1), [Zn(1,4-bdc)(bphc)]‧DMF (2), [Zn(1,4-bdc)(bphc)]‧2H2O (3) and [Zn((OH)2-1,4-bdc)(bphc)] (4). Compounds 1, 2 and 4 are two-dimensional layer structure with two-fold interpenetration, and compound 3 is a three-dimensional net structure with four-fold interpenetration.
In the cation sensing experiments, the H2O suspensions of 1 and 3 showed excellent specificity and quenching efficiency toward Fe3+ ions. In addition, the DMF suspension of 3 exhibited strong fluorescence intensity, which would be quenched by Cu2+, Al3+, Cr3+ and Fe3+ ions in different degrees of quenching efficiency. Of note, the titration sensing experiments of 3 in detecting trivalent metal ions showed a two-stage sensing behavior. The H2O suspensions of 4 emitted weak fluorescence, which could selectively detect Al3+ ions through fluorescence enhancement effect. Interference experiments and detection limit measurements confirmed that compounds 1, 3, and 4 have good metal ion sensing performances with high selectivity and low detection limits. As a result compounds 1, 3, and 4 can be used as good fluorescent sensing materials toward metal ions.
In the detection experiments of small organic molecules such as phenols and amines, the H2O suspension of 1 displayed no obvious quenching effect. However the DMF suspension of 3 showed good sensing specificity toward p-phenylenediamine, and could selectively distinguish p-phenylenediamine from the o-, m- and p-phenylenediamine. The good sensitivity and low detection limit promote 3 to be used as a good p-phenylenediamine sensing material.

並列關鍵字

metal–organic framework ； fluorescence ； sensing ； zinc

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