以萘醯亞胺雙吡啶與芳香二酸製備金屬有機框架化合物：合成、結構鑑定、氣體吸附與硝基化合物及離子感測

金屬有機框架化合物[Zn(Br-1,3-bdc)(NI-mbpy-34)] (1)、[Cd(Br-1,3-bdc)(NI-mbpy-34)(H2O)]·2H2O (2)和[Cd((OH)2)-1,4-bdc)(NI-mbpy-34)2] (3) 以萘醯亞胺雙吡啶橋接配體N-(pyridin-3-ylmethyl)-4-(pyridine-4-yl)-1,8-naphthalimide (NI-mbpy-34) 分別與不同金屬鹽類和二酸化合物在二甲基甲醯胺和水混合溶液的媒介下經溶劑熱法所合成。化合物 1 結晶於單斜晶系(monoclinic)，空間群為 C2/c ，經由 NI-mbpy-34 和 Br-1,3-bdc 的連結，形成三維網狀結構，無孔洞性 (孔洞率為 0.6%)。化合物 2 結晶於三斜晶系 (triclinic)，空間群為 P1 ̅ ，經由 NI-mbpy-34 和 Br-1,3-bdc 的連結，形成二維格子狀結構。孔洞率為 9.8%，可應用於氮氣、二氧化碳的吸脫附。化合物3結晶於三斜晶系，空間群為P1 ̅，經由NI-mbpy-34和(OH)2-1,4-bdc的連結形成二維格子狀結構，無孔洞性。化合物1-3在懸浮溶液都有良好的螢光表現，可用於檢測硝基化合物、金屬離子、陰離子等。在感測硝基化合物方面，化合物1-3皆對芳香性的硝基化合物有著較好良好的螢光焠熄，對非芳香類的硝基化合物焠熄效果皆較差，有選擇性感測的潛力；在陰離子檢測方面，化合物1-3皆對Cr2O72-和CrO42- 離子有著非常良好的螢光焠熄效果，同時在有干擾離子的情況下，依舊對Cr2O72-和CrO42- 離子有著良好的焠熄效果，表示化合物1-3是檢測這兩個離子很好的材料；在金屬陽離子檢測方面，化合物1對Cr3+有良好的螢光增強效果，並且在干擾離子的存在下，依舊有良好的螢光增強效果，對Cr3+離子有很好的檢測效果；化合物2-3對Cr3+、Al3+及Fe3+皆有良好的螢光增強效果，化合物2在有干擾離子的存在下，依舊對Cr3+、Al3+及Fe3+有著良好的螢光增強效果，對著三個離子有良好的檢測效果；化合物3在有干擾離子的存在下，只對Cr3+及Al3+有保持著良好的螢光增強效果，Fe3+會受到干擾離子的影響，表示化合物3對Cr3+及Al3+有著較好的檢測效果，對Fe3+並不能做複雜的檢測。同時，我們也計算了化合物1-3對有明顯螢光增強或焠熄效果的離子的偵測極限，結果表示，化合物1-3對有明顯螢光增強效果的Cr3+、Al3+及Fe3+ 離子，有著良好的偵測極限，大約在1-4 μM左右；化合物1-3對有明顯螢光焠熄效果的Cr2O72-和CrO42- 離子，也有著不錯的偵測極限，最低可達5 μM，最高至50 μM。最後，我們對化合物2進行了N2與CO2的氣體吸附，結果顯示吸附效果並不佳。

關鍵字

金屬有機框架；硝基化合物；陰離子感測；陽離子感測；螢光

並列摘要

Metal-organic frameworks [Zn(Br-1,3-bdc)(NI-mbpy-34)] (1)、[Cd(Br-1,3-bdc) (NI-mbpy-34)(H2O)]·2H2O (2) and [Cd((OH)2)-1,4-bdc)(NI-mbpy-34)2] (3) are constructed from imide-based bispyridyl ligand N-(pyridin-3-ylmethyl)-4-(pyridin-4-yl)-1,8-naphthalimide (NI-mbpy-34) with different metal ions and aromatic dicarboxylic acids in DMF-water media under hydrothermal reactions. Compound 1 crystallizes in monoclinic space group C2/c; the Zn(II) centers are connected by the NI-mbpy-34 and Br-1,3-bdc to form a 3D condense network having no porosity. Compound 2 crystallizes in triclinic space group P1 ̅; the Cd(II) centers are connected by the NI-mbpy-34 and Br-1,3-bdc to form a 2D grid-like structure with porosity of 9.8%. Compound 3 crystallizes in triclinic space group P1 ̅; the Cd(II) centers are connected by the NI-mbpy-34 and (OH)2-1,4-bdc to form a 2D grid-like structure having no porosity. Compounds 1-3 in solvent suspensions all exhibit strong fluorescence emissions, which are potentially applied in the detection of nitro compounds, cations, and anions. In the detection of nitro compounds, compounds 1-3 exhibit remarkable fluorescence quenching with addition of aromatic nitro compounds, while insufficient fluorescence quenching toward aliphatic nitro compounds. In the detection of anions, compounds 1-3 exhibit remarkable fluorescence quenching with addition of dichromate (Cr2O72-) and chromate (CrO42-), even in the presence of interfering ions, meaning that compounds 1-3 are great materials for detection of dichromate and chromate. In the detection of cations, compound 1 shows remarkable fluorescence enhancement with addition of Fe3+, even in the presence of interfering ions. Compounds 2 and 3 exhibit remarkable fluorescence enhancement with addition of Al3+、Cr3+ and Fe3+. The anti-interference measurements show that with the exception of 3 towards Fe3+, other cases all display good anti-interference ability. We also try to determine the limit of detection (LOD) of compounds 1-3 for sensing ions. The results show that compounds 1-3 have low LODs of about 1-4 μM for cations and 5-50 μM for dichromate and chromate.