以雙吡啶萘亞醯胺、多酸根與鋅金屬製備配位聚合物：合成、結構
鑑定與硝基化合物檢測

利用雙萘啶橋接配子NI-bipy-34與多酸化合物在水熱條件下，得到五種鋅金屬配位聚合物：{[Zn2(2,6-ndc)(2,6-Hndc)2(NI-bipy-34)]2·H2O}n（1），[Zn(2,6-ndc)(H2O)]n（2），[Zn(1,4-Hbdc)(1,4-bdc)0.5(NI-bipy-34)]n （3），[Zn(5-NH2-1,3-bdc)(H2O)]n（4），{[Zn(1,3,5-Hbtc)(NI-bipy-34)(H2O)]·H2O}n（5）。化合物1為二維三次互穿結構；化合物2為三維結構；化合物3為一維梯子狀結構；化合物4為二維蜂巢狀結構；化合物5為二維格子狀結構。利用化合物1-5的螢光性質來進行硝基化合物的檢測。在硝基的檢測實驗中，可以發現硝基苯對於化合物1、3、5有明顯(60-80%)的螢光焠熄效果，而1,4-二硝基苯則是對於化合物2、3、5有不錯(30-50%)的螢光焠熄效果。在陽離子交換的實驗中，我們利用後合成修飾的方式將化合物2、5中的鋅離子部分交換成銅離子，得化合物2-Cu、5-Cu，並利用感應偶合電漿質譜進行動力學偵測陽離子交換速率。此外，化合物2經由鈷離子交換後會產生結構變化，得到一維線性結構的鈷配位聚合物，化合物2-Co。將化合物1-5、2-Cu、5-Cu浸泡於染料水溶液中，利用可見光－紫外光光譜檢測化合物對染料的吸附能力。結果顯示化合物1-5、2-Cu、5-Cu無法吸附染料AO7、甲基橙、亞甲藍，但化合物1、2、4、5-Cu與化合物1、4在較長時間浸泡下會分別對甲基藍與甲基綠有吸附的效果。

關鍵字

配位聚合物；化學感測器；螢光

並列摘要

Reactions of N-(pyridin-3-yl)-4-(pyridin-4-yl)-1,8-naphthalimide (NI-bipy-34), Zn(NO3)2·6H2O and multicarboxylic acids (2,6-naphthalenedicarboxylic acid, 2,6-H2ndc; 1,4-benzenedicarboxylic acid, 1,4-H2bdc; 5-aminoisophthalic acid, 5-NH2-1,3-H2bdc; 1,3,5-benzenetricarboxylic acid, 1,3,5-H3btc) in N,N-dimethylformamide (DMF)-H2O media under hydro(solvo)thermal conditions afforded zinc–organic networks, {[Zn2(2,6-ndc)(2,6-Hndc)2(NI-bipy-34)]2·H2O}n (1), [Zn(2,6-ndc)(H2O)]n (2), [Zn(1,4-Hbdc)(1,4-bdc)0.5(NI-bipy-34)]n (3), [Zn(5-NH2-1,3-bdc)(H2O)]n (4), {[Zn(1,3,5-Hbtc)(NI-bipy-34)(H2O)]·H2O}n (5). Compound 1 has a three-fold interpenetrated 2D layered structure; compound 2 has a 3D structure; compound 3 has a 1D ladder structure; compound 4 has a 2D honeycomb structure; compound 5 has a 2D square grid structure. 　　Compounds 1-5 exhibit intense photoluminescence with λmax of 400-550 nm, making them useful for detecting nitro compounds. Experimental results of nitro compound detection have shown that nitrobenzene would cause significant (60-80%) fluorescence quenching in the cases of compounds 1, 3 and 5, whereas 1,4-dinitrobenzene showed 30-50% fluorescence quenching in the cases of compounds 2, 3 and 5. Cation-exchange experiments showed that Zn2+ ions in compounds 2 and 5 would be partially exchange by Cu2+ ions, through post-synthetic modification (PSM), resulting in isomorphous compounds 2-Cu and 5-Cu, respectively. Otherwise, Co2+-exchanged experiments showed that Zn2+ ions in compound 2 would be exchanged, resulting compound 2-Co in a one-dimensional chain structure. Dye adsorption experiments of compounds 1-5, 2-Cu and 5-Cu have shown that there are no adsorptive behaviors between designed coordination polymer materials and part of these dye (AO7, MO, MB). In longer time of soak(1 to 3 days), methyl blue would be adsorbed by compounds 1, 2, 4, 5-Cu and MG would be adsorbed by compounds 1, 4 respectively.