以苯並噻二唑雙吡啶與芳香多酸製備鎘金屬有機框架化合物：合成、結構鑑定及陰、陽離子感測

Cadmium Based Metal-Organic Frameworks Constructed from Di(pyridin-4-yl)benzothiadiazole and Aromatic Multicarboxylic Acids: Synthesis, Structures, and Detection of Anions and Metal Ions

江祈瑨(Qi-Jin Jiang)

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/ncnu202100216

摘要

本研究透過鈴木偶聯反應合成出新穎有機配體苯並噻二唑雙吡啶(bis(pyridin-4-yl)benzothiadiazole，BTD-bpy)，再利用此有機配體與硝酸鎘及芳香多酸化合物透過溶劑熱合成法製備出二個金屬有機框架化合物，分別為 [Cd3(BTD-bpy)2(btc)2] (1，H3btc = 1,3,5-benzenetricarboxylic acid) 、 [Cd2(BTD-bpy)2(1,4-ndc)2] (2，1,4-H2ndc = 1,4-naphthalenedicarboxylic acid)，並且與本實驗室已合成之金屬有機框架 [Zn2(BTD-bpy)(Hbtc)2(MeOH)2] (3) 與 [Zn4(BTD-bpy)2(1,4-ndc)4] (4) 進行螢光感測比較。
化合物1、2、4為三維層柱狀結構，皆以BTD-bpy作為層與層之間的橋接配位基，其中，化合物2、4具有二次互穿的結構；化合物3為二維層狀結構。
在陽離子感測方面，將化合物1 - 4配製成懸浮液後，化合物1、2對銀、鋁、鉻、鐵等離子有相似的感測行為；化合物3、4皆對鐵離子具有螢光焠熄的效果。在陰離子感測方面，將化合物1 - 4配製成懸浮液後，發現四者皆對CrO42-、Cr2O72-、MnO4-陰離子表現明顯的螢光焠熄效應，經由干擾離子實驗以及定量滴定實驗中可得知，化合物1 - 4皆對上述離子具有不錯的選擇性離子感測表現以及低偵測濃度，顯示化合物1 - 4可做為良好的離子螢光感測材料。

關鍵字

螢光感測 ； 陽離子 ； 陰離子

並列摘要

A new organic ligand bis(pyridin-4-yl)benzothiadiazole (BTD-bpy) was synthesized by Suzuki-coupling, which was used to assemble with cadmium nitrate and aromatic multicarboxylic acid to form two new metal-organic frameworks (MOFs), namely [Cd3(BTD-bpy)2(btc)2] (1，H3btc = 1,3,5-benzenetricarboxylic acid) and [Cd2(BTD-bpy)2(1,4-ndc)2] (2，1,4-H2ndc = 1,4-naphthalenedicarboxylic acid)。Compounds 1 and 2 together with Zn MOFs [Zn2(BTD-bpy)(Hbtc)2(MeOH)2] (3) and [Zn4(BTD-bpy)2(1,4-ndc)4] (4), synthesized in our laboratory previously were used as platforms applying in fluorescence sensing.
Compounds 1, 2 and 4 are three-dimensional pillared-layer structures, wherein the BTD-bpy as the bridging pillars linked adjacent layers of Cd-carboxylate layers；of note, 2 and 4 are two-fold interpenetrating while 1 is non-interpenetrating. On the other hand, compound 3 has a two-dimensional layer structure.
In terms of cation sensing, compounds 1 and 2 have similar sensing behaviors toward Ag+、Al3+、Cr3+ and Fe3+ in H2O suspensions while compounds 3 and 4 show remarkable fluorescence quenching effect toward Fe3+ in DMF suspensions. In terms of anion sensing, all of the four compounds exhibit significant fluorescence quenching effect towards CrO42-, Cr2O72-, and MnO4- anions. Through anti-interference and quantitative titration experiments, it could be found that compounds 1−4 all have good selectivity, high sensitivity and low detection limit for detective sensing of above-mentioned ions. As a result, compounds 1−4 can be utilized as good ion fluorescence sensing materials.

並列關鍵字

fluorescence sensing ； cation ； anion

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